Positive photoresist composition

专利摘要:
The positive photoresist composition consists of a photo-acid generator and a special resin. The resin contains repeating units each having a group represented by formula (I): -SO 2 -OR- (Ⅰ) R represents an optionally substituted alkyl, cycloalkyl and alkenyl group, which increases the dissolution rate in the alkaline developer by the action of an acid and is protected by or specifically defined by partial structures containing alicyclic hydrocarbons. It contains an alkali-soluble group represented by at least one of (pVI), which is decomposed by the action of an acid to increase solubility in alkali. The latter is used as a complex with compounds that decompose under the action of acids to generate sulfonic acids.
公开号:KR20000047927A
申请号:KR1019990055067
申请日:1999-12-06
公开日:2000-07-25
发明作者:사토켄이치로오；오하시히데카주；코다마쿠니히코；아오아이토시아키
申请人:무네유키 가코우；후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

Positive Photoresist Composition {POSITIVE PHOTORESIST COMPOSITION}
The present invention relates to positive photoresist compositions for use in ultramicrolithographic processes in the manufacture of ULSI and high performance microchips or other photo productions. More specifically, the present invention relates to an ultra-violet region including a positive photoresist composition having excellent defocus latitude determined by photosensitivity or line-pitch and an excimer laser beam, in particular a light beam having a wavelength of 250 nm or less. It relates to a positive photoresist composition for forming an ultrafine pattern of light rays having an internal wavelength.
The degree of integration of ICs (integrated circuits) has been increasingly improved in recent years, and the formation of ultrafine patterns having a line width of 0.5 nm or less has been required in manufacturing USLI and other semiconductor substrates. Due to this tendency, the exposure wavelength of the light source used for photolithography is getting shorter and shorter to meet the above requirement, and the excimer laser having a short wavelength in far ultraviolet light (eg XeCl, KrF, ArF excimer laser) The use of light is currently under consideration.
The type of lithographic pattern formed in the above wavelength range is chemically amplified.
Generally, chemically amplified resists can be roughly divided into three systems, for example, two-component, 2.5-component, and three-component systems. The two-component system consists of a complex of a compound that generates an acid upon photolysis (hereinafter referred to as a photo-acid generator) and a binder resin. These binder resins have groups which decompose to the molecule by the action of an acid which doubles the solubility of the resin in an alkaline developer (the group refers to an acid-degradable group). The 2.5-component system consists of such a two-component system containing more of a low molecular compound having an acid-decomposable group. The three-component system consists of a photo-acid generator, an alkali-degradable resin, and the low molecular compound mentioned above.
Such chemically amplified resists must meet the requirements of any particular light source, either ultraviolet or far-infrared, even if they are suitable for photoresists for ultraviolet or ultraviolet radiation. For example, the resist composition contains a polymer obtained by bonding an acetal group or a ketal group to a hydroxystyrene polymer as a protecting group and a polymer showing reduced absorbance when using a KrF excimer laser having a wavelength of 248 nm. Has been proposed. The above example is disclosed in JP-A-2-141636 (where "JP-A" means "unexamined, published Japanese patent application"), JP-A-2-19847, JP-A-4-219757 and JP-A-5-281745. Furthermore, similar compositions in which t-butoxycarbonyloxy and p-tetrahydropyranyloxy groups are used as the acid-decomposable group are disclosed in JP-A-2-209977, JP-A-3-206458, JP-A-2. It's at -19847.
Although such a precursor art composition is suitable for the irradiation of 248 nm KrF excimer laser light, it can be seen that the ArF excimer laser has insufficient sensitivity when used as a light source because it has excellent absorption power. Such compositions have drawbacks that involve low sensitivity, such as decay in sharpness and out of focus latitude, pattern profiles and the like. Therefore, the precursor art composition still needs to be improved in many respects.
As a result, there has been a proposal to use a resin having an alicyclic hydrocarbon structure bonded therein to the photoresist composition which is an ArF excimer laser light source to impart dry-etch resistance. However, this type of system has high hydrophobicity as one of the various effects that result from the bonding of alicyclic hydrocarbon structures. As a result, resists containing such resins are for example. The resist has such drawbacks that it is difficult to develop in aqueous tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution, which has been commonly used as a resist developing solution, but the resist strips off the substrate during development.
Methods of copying such hydrophobic resists are examined. Among them, there is also a method of injecting an organic solvent such as isopropyl alcohol into the developer. Such a measurement shows that, for example, there is an unresolved problem in the expansion of a resist film or a process problem.
In order to improve this point of resist, many attempts have been made to compensate for the deficiencies of various hydrophobic alicyclic hydrocarbon structures by combining hydrophilic groups.
A photoresist composition of another ArF light source consists of a composite of an acrylic resin that exhibits reduced absorbance than a partially hydrated styrene resin and a compound that generates an acid upon light irradiation. Such compositions are disclosed in the following JP-A-7-199467 and JP-A-7-252324 examples. In particular, JP-A-6-289615 discloses a resin containing a carbon group each having a tertiary carbon atom and an acrylic acid basic unit which is bonded to one of oxygen atoms in a carboxy group via an ester bond.
JP-A-7-234511 discloses acid-degradable resins containing repeating units derived from acrylic esters or fumaric esters. However, the disclosed resist composition is inadequate in terms of pattern profile, adhesion to the substrate, and other aspects. Therefore, none of the precursor art photoresist compositions have ever been preferably used as an ArF light source.
JP-A-9-73173, JP-A-9-90637, and JP-A-10-161313 disclose resist materials containing acid-reactive compounds, which also include alicyclic groups. It contains an alkali-soluble group protected by a structure containing and a structural basic unit produced upon removal of the protecting group by the action of an acid.
Although methods for using various resins having acid-decomposable groups in the chemically amplified photoresist described above have been studied, there is room for improvement.
For example, recent inventions tend to contain a variety of patterns, thereby requiring the resist to have many effects on defocusing latitude, which depends on the line pitch. The invention also has a pattern area in which the lines are densely distributed and a pattern area in which the lines are divided by a wider space than the line, or even an isolated line. Therefore, it is important to dissolve various lines with high reproducibility. However, line melting is not always easy due to optical factors, and the method of desirably regenerating based on the improvement of the resist also remains opaque.
As described above, resins containing acid-decomposable groups used in photoresist for far ultraviolet exposure generally contain alicyclic hydrocarbon groups in addition to acid-decomposable groups.
This is because these resins are hydrophobic and have a problem that spreads. Although various methods described above have been considered to alleviate such problems, the above techniques are still insufficient in many aspects (especially developability), and improvement is required.
Meanwhile, JP-A-8-248561 discloses a photoreactive composition consisting of a photo-acid generator and an acid-doubling agent, wherein the acid-doubling agent is produced by the action of acid generated by the photo-acid generator. Generates. In addition, Vol. 3049, pages 76-82 of SPIE, disclose chemically amplified resists for 193-nm lithography consisting of acid-generating agents, partially protected alicyclic polymers, and acid-doubling agents.
However, the above-described technique relating to a light source emitting far-ultraviolet short wavelength light, such as an ArF excimer laser (193 nm), still has room for improvement in its developability, and in detail, defects and scum of the developer itself ( Development wastes). In addition, improvement is required in the problem regarding the reproduced line width, such as the problem that the line width is diversified with pattern formation.
The first object of the present invention is to eliminate the problem of improvement of original action, especially in the production of the microphotographic product described above used for far ultraviolet light such as KrF or ArF excimer laser. In particular, it is a first object to provide a high sensitivity positive photoresist composition which reduces the occurrence of developing residues and a positive photoresist composition having good defocusing latitude that depends on the line pitch.
A second object of the present invention is to eliminate the problem of the improvement of the original action of the microphotographic product described above, which is particularly used as far ultraviolet light such as KrF or ArF excimer laser. In detail, it is a second object to provide a positive photoresist composition which is free of defects during development and free of problems such as scum generated during development. It is a further object of the present invention to provide a photoresist composition of ultraviolet light having a line width excellent in reproducibility.
The present inventors have made intensive studies on the components of the chemically amplified positive resist fluid. Thereby, it was found that the first object of the present invention is realized by using a special acid-decomposable resin. The present invention has been carried out on the basis of this finding.
In other words, the first object of the invention was carried out in the following manner.
(1) Composition of Positive Photoresist Composition
It consists of a compound which generates an acid when irradiated with actinic radiation or radiation and a resin containing a group represented by the general formula (I) as a repeating unit, which increases the dissolution rate in alkaline developer due to the action of acid.
-SO ₂ -OR- (Ⅰ)
(R represents optionally substituted alkyl, cycloalkyl and alkenyl groups.)
The inventors have intensively studied the components of the chemically amplified positive photoresist composition. It was thus found that the second object of the present invention is realized by the use of special acid-degradable resins and additives. The present invention has been carried out on the basis of this fact,
In other words, the second purpose was performed in the following manner.
(2) The positive photoresist composition for exposure to ultraviolet rays is protected by a partial structure containing an alicyclic hydrocarbon, a compound which generates an acid upon irradiation with actinic rays and radiation, or at least one of the following general formulas (pI) to (pVI). It consists of a resin containing an alkali-soluble group represented, which is decomposed by the action of an acid which increases solubility in alkali. In addition, the composition consists of a compound which is also degraded by the action of an acid producing sulfonic acid.


(R ₁₁ represents a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group bonded to a carbon atom.);
If at least one of R _{12 to} R ₁₄ and any one of R ₁₅ and R ₁₆ represent an alicyclic hydrocarbon group, R ₁₂ to R ₁₆ each represent a linear and branched alkyl group having 1 to 4 carbon atoms;
If at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group and one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group, then R ₁₇ and R ₂₁ represents linear and branched alkyl groups and alicyclic hydrocarbons each having a hydrogen atom and 1 to 4 carbon atoms;
If at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group, R ₂₂ to R ₂₅ each independently represent a linear and branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
(3) As described in (2) above, the positive photoresist composition for far ultraviolet exposure contains fluorine or a silicone surfactant.
The compounds used in the present invention will be described in detail below.
It contains the repeating unit which has group represented by general formula (I). Resin (also known as acid-decomposable resin) whose dissolution rate increases in alkaline developer due to acid action:
The acid-degradable resin used in the present invention is characterized by having a repeating unit having at least one group represented by -SO ₂ -OR-.
In the case of an alkyl group represented by R in formula (I), this includes linear and branched alkyl groups, which may be substituted one or more. The linear and branched alkyl groups preferably contain 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. The most effective examples in that regard are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl. Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl.
Examples of cycloalkyl groups include groups having 3 to 30 carbon atoms or containing heteroatoms such as oxygen and nitrogen. Detailed examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, and admanthyl. Norbornyl, bonyl, tricyclodecanyl, dicyclotenyl, norbornane-epoxy, menthyl, isomentyl, neomentyl, tetracyclododecanyl, steroid residues, tetrahydropyranyl, morpholino.
Alkenyl groups include those having 2 to 6 carbon atoms or one or more substituents.
Detailed examples thereof include vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, 3-oxocyclohexenyl. Of these alkenyl groups, each cyclo group may contain one or more oxygen atoms.
Examples of the substituents of the alkyl, cycloalkyl and alkenyl groups described above include a carboxy, acyloxy group, cyano, alkyl group, substituted alkyl group, aryl group, halogen atom, hydroxy, alkoxy group, acetyl amido, alkoxycarbonyl group , You know. Examples of the alkyl group include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclobutyl, and cyclopentyl. Examples of substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups, and examples of alkoxy groups such as alkoxy groups or alkoxycarbonyl groups include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups. have. An example of the acyloxy group is acetoxy. Examples of aryl groups include. Optionally substituted aryl groups having 9 to 10 carbon atoms, such as phenyl, toryl, naphthyl, etc.
Preferable examples of the repeating unit having a group represented by General Formula (I) include a repeating unit represented by the following General Formula (II).
General formula (Ⅱ)
(In general formula (II), R ₁ to R ₃ are each independently a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or a group represented by -SO ₂ -OR. Z is a single bond, an ether group, an ester group, An amino group, an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, or a divalent group consisting of two or more thereof, wherein R is the same as defined above.
Examples of the alkyl group and halogen atom represented by R ₁ to R ₃ include the same alkyl group and halogen atom as in the examples of R listed above.
Examples of the alkylene group and the substituted alkylene group include groups represented by the following examples.
-[C (R) _a (R) _b ] _r-
In the above formula, R _a and R _b are the same or different and each represents a halogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxy, or an alkoxy group.
Preferred examples of the alkyl group include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, and substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups. Examples of the alkoxy group are methoxy. Some have 1 to 4 carbon atoms such as ethoxy, propoxy, butoxy, and the halogen atom. Chlorine, bromine, fluorine and iodine atoms. In addition, r is an integer of 1-10.
The arylene group includes a substituted arylene group and an arylene group, and examples thereof include those having 6 to 10 carbon atoms such as phenylene, tolylene and naphthylene. Substituents of a substituted arylene group include a carboxy, acyloxy, cyano, alkyl group. Substituted alkyl groups. Halogen atom. Hydroxyl, alkoxy group, acetylamido, alkoxycarboxyl group, acyl group. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, and substituted alkyl groups include hydroxyl. There are a halogen atom and an alkoxy group, and in the alkoxy group, methoxy. Ethoxy. Some have 1 to 4 carbon atoms, such as propoxy and butoxy. The acyloxy group includes acetoxy, examples of the halogen atom include chlorine, bromine, fluorine and iodine, and detailed examples of the monoliths corresponding to the repeating unit having a group represented by the general formula (I) are shown below. However, the content of the present invention is not limited only to this example.


In the present invention, the acid-decomposable resin contains a group that is decomposed by the action of an acid (or also called an acid-decomposable group).
Examples of acid-decomposable groups are represented by -COOA ⁰ or -OB ⁰ . Examples of groups containing such groups are represented by -R ⁰ -COOA ⁰ or -Ar-OB ⁰ .
Wherein A ⁰ is -C (R ¹ ) (R ² ) (R ³ ), -Si (R ¹ ) (R ² ) (R ³ ), -C (R ⁴ ) (R ⁵ ) -OR ⁶ or It is represented by a lactone group. B ⁰ is represented by -A ⁰ or -CO-A ⁰ .
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ⁶ represents an alkyl group, a cycloalkyl group or an aryl group Display. However, two of R ¹ to R ³ are not hydrogen atoms, two of R ¹ to R ³ are bonded to each other to form a ring, and also two of R ⁴ to R ⁶ are also bonded to each other to form a ring. R ⁰ represents a single bond or a divalent or expensive partially substituted aliphatic and aromatic hydrocarbon group, and -Ar- represents a divalent or expensive partially substituted mono, polycyclic aromatic group.
Preferred examples of the alkyl group include one to four carbon atoms such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl and the like, and preferred examples of the cycloalkyl group are cyclopropyl, cyclobutyl, cyclobutyl And those having 3 to 10 carbon atoms, such as cyclohexyl and admantyl. Preferred examples of the alkenyl group include those having 2 to 4 carbon atoms such as vinyl, propenyl, allyl and butenyl, and preferred examples of the aryl group include phenyl, cyryl, toluyl, cumenyl, naphthyl and anthracenyl. And a cycloalkyl group include cyclopropyl, cyclopentyl, cyclohexyl, admantyl, norbornyl, carbonyl, tricyclodecanyl, dicyclopentenyl, and the like. Some have 3 to 30 carbon atoms, such as norbornane-epoxy, menthyl, isomentyl, neomentyl, tetracyclodecanyl, and steroid residues. Examples of aralkyl groups include partially substituted aralkyl groups having 7 to 20 carbon atoms, such as benzyl, phenethyl, cumyl and the like.
Examples of substituents include hydroxy, halogen atoms (fluorine, chlorine, bromine, iodine), nitro, cyano, alkyl groups mentioned above, methoxy, ethoxy, hydroxylethoxy, propoxy, hydroxylpropoxy, n- Alkoxy groups such as butoxy, isobutoxy, sec-butoxy, t-butoxy, acyl groups such as formyl, acetyl, butyryl, benzoyl, cyanyl, and bareryl; acyloxy groups such as butyryloxy, and an alkenyl group described above And aryloxy carbonyl groups such as aryloxy groups such as phenoxy and benzoyloxy.
Examples of the lactone group include groups having the following structure.
In the above formula, R ^a , R ^b and R ^c each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 4;
When an ArF excimer laser is used for exposure, the acid-decomposer will probably be represented by -C (= 0) -X ₁ -R ₀ . In this formula, examples of R ₀ include tertiary alkyl groups such as t-butyl, t-amyl and isobornyl, and 1-ethoxyethyl, 1-butoxylethyl, 1-isobutoxylethyl, 1-cyclohexenyloxyethyl and the like. And a lactone group described above with an alkoxymethyl group such as 1-alkoxyethyl group and 1-methoxymethyl, 1-ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, trialkylsilyl group, and 3-oxocyclohexyl. X ₁ represents oxygen or a sulfur atom, and more preferably an oxygen atom.
Resin containing at least one group is represented by general formula (I), and an acid-decomposable group needs to have a structure suitably selected according to the use of exposure.
In the case of using a KrF excimer laser having a wavelength of 248 nm for exposure, the resin preferably includes repeating units containing benzene rings such as styrene-derived repeating units as main repeating units.
When using a KrF excimer laser having a wavelength of 193 nm for exposure, a repeating unit having a benzene ring cannot be used. In such a case, it is preferable to contain an alicyclic structure in the main or sub chain associated with it as a main repeating unit.
Acid-degradable resins suitable in the case of using a KrF excimer laser having a wavelength of 248 nm for exposure are described below.
In this regard, the side chain is an alkali-soluble resin having a basic resin and having a repeating unit represented by the general formula (I) and an acid-decomposable group having an -OH or -COOH group, in particular -R ⁰ -COOH or A _r -OH group. Alkali-soluble resin which has a side chain is more preferable.
Such alkali-soluble resins have alkali solubility, which is preferably 170 Å / sec or higher, and 330 Å / sec or higher as measured by 0.261 N tetramethylammonium hydroxide (TMAH) at 23 ° C. Even better.
In order to obtain a rectangular profile, an alkali-soluble resin which is very easy to transmit by far ultraviolet rays or excimer laser light is preferable. In detail, it is preferable that the alkali-soluble resin of the 1 micrometer-thick film has a transmission rate of 35% or more at 248 nm.
In particular, alkali-soluble resins which are preferable in this respect are polymers (o-, m-, p-hydroxystyrene), copolymers of such hydroxystyrenes, hydrotreated polymers (hydroxystyrene), halogens And alkyl-substituted polymers (hydroxystyrene), partially o-alkylated and, o-acylated polymers (hydroxystyrene), styrene / hydroxystyrene copolymers, -Methylstyrene / hydroxystyrene copolymers, hydrogenated novolic resins.
The resin having an acid-decomposable group used in the present invention can be obtained by reacting a given alkali-degradable resin with an alkali-soluble resin having a precursor of an acid-decomposable group or copolymerizing a monomer, and also having various monomers in a given resin. And an acid-degradable group can be obtained, and the monomers are disclosed in European Patent 254,853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. have.
Detailed examples suitable as acid-decomposable resins when using KrF excimer laser light having a wavelength of 248 nm as exposure will be shown below. However, the resin used in the present invention is not limited to this example.


In the case of using a KrF excimer laser having a wavelength of 193 nm for exposure, a resin having a main repeating unit containing an alicyclic structure as well as a benzene ring in the main or sub chain, respectively, is preferable.
The alicyclic structure may be monocyclic or polycyclic. For example, the resin may have a monocyclic-, bicyclic-, tricyclic-, tetracyclic structure having five or more carbon atoms. The alicyclic structure preferably has 6 to 30 carbon atoms, more preferably 7 to 25 carbon atoms. The alicyclic hydrocarbon group has one or more substituents. Examples of alicyclic structures include cyclopentane. Cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane and the following structures are provided.
In the above structure cyclopentane, cyclohexane, (5), (6), (7), (9), (10), (13), (14), (15), (23), (28), (36), (37), (42) and (47) are preferable.
Substituents of an alicyclic structure include an alkyl group, a halogen atom, a hydroxy, an alkoxy group, a carbonyl, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl or butyl, and an alkyl substituent selected from the group consisting of methyl, ethyl, propyl and isopropyl is more effective. Substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups, and alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy.
Preferred examples of the acid-decomposable resins include the following ① to ③.
(1) Resin containing an alicyclic structure and an acid-decomposable group in a repeating unit in the group represented by the general formula (I) and its side chains.
(2) A resin containing a repeating unit having an alicyclic structure in the group represented by the general formula (I), an acid-decomposable group, and its side chain.
(3) A resin having an alicyclic structure in the group represented by the general formula (I) and its side chain and containing an acid-degradable group as a repeating unit.
As for the resin of Example ①, the polymer represented by the following general formula (Ia) is preferable.
General formula (Ⅰa)
In general formula (Ia), R <_1> -R <_3> and R, Z have the same meaning as in general formula (I) and (II), respectively. B ₁ represents a monovalent alicyclic group and R _X represents an acid-decomposable group. R ₁₀ ′ represents a linear or branched alkyl group having the same or different hydrogen atoms and optionally substituted 1-4 carbon atoms.
Examples of the monovalent alicyclic group represented by B ₁ include the monovalent residues of the alicyclic structure described above.
Examples of the acid-decomposable group represented by R _X include the acid-decomposable group described above.
Resin of Example ② is preferably a polymer represented by the following general formula (Ib).
General formula (Ⅰb)
In general formula (Ib), R <_1> -R <_3> and R, Z have the same meaning as in general formula (I) and (II), respectively. R ₁₀ ′ represents a linear or branched alkyl group having the same or different hydrogen atoms and optionally substituted 1-4 carbon atoms. Y represents a single component or a complex consisting of two or more components selected from a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, and an ester group.
Ra represents at least one group made from the groups represented by the following formula (RaI) in (RaVI).
In formulas (RaI) to (RaVI), R ₁₁ represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and cec-butyl, and Z ₁ is bonded to a carbon atom to form an alicyclic group Mark the atomic groups needed to do this.
If at least one of R ₁₂ to R ₁₄ or one of R ₁₅ and R ₁₆ represents an alicyclic group, R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.
If at least one of R ₁₇ to R ₂₁ represents an alicyclic group, and any one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group or alicyclic group having 1 to 4 carbon atoms, R ₁₇ to R ₂₁ represents Each independently represents a hydrogen or a linear or branched alkyl or alicyclic group having from 1 to 4 carbon atoms.
R ~ ₂₂ faces at least one of R ₂₅ represents an alicyclic group, each of R ₂₂ ~ R ₂₅ are individually displayed or a linear alkyl group or alicyclic group of the side chain with 1 to 4 carbon atoms.
In formulas (RaI) to (RaVI), the alkyl group represented by R ₁₂ to R ₂₅ is an optionally substituted linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl.
Examples of the substituent of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine, bromine, iodine atom), an acyl group, acyl group, alkoxy group, cyano, hydroxy, carbonyl, alkoxycarbon There are Nyl and Nitro.
The alicyclic group represented by R ₁₁ to R ₂₅ and the alicyclic group forming Z together with each carbon atom may be monocyclic or polycyclic. Examples thereof include groups having a monocyclic, bicyclic, tricyclic or tetracyclic structure having five or more carbon atoms. Such alicyclic group preferably has 6 to 30 carbon atoms, more preferably 7 to 25 carbon atoms. Such alicyclic groups have one or more substituents.
As examples of the alicyclic structure in the general formulas (RaI) to (RaVI), adenmentyl, nordemanyl, decalin residue, tricyclodecanyl, tetracyclodecanyl, norbornyl, sedorol residue, cyclohexyl and cycloheptyl , Cyclooctyl, cyclodecanyl, cyclododecanyl.
Examples of substituents of such alicyclic groups include alkyl groups, substituted alkyl groups, halogen atoms, hydroxy, alkoxy groups, carbonyl, alkoxycarbonyl groups, and preferred examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, Most preferably, the alkyl substituent is selected from the group consisting of methyl, ethyl, propyl, isopropyl. Examples of substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups, and examples of alkoxy groups include methoxy, ethoxy, propoxy and butoxy having 1 to 4 carbon atoms.
In addition to the acid-decomposable group represented by COORa, it is preferable that the polymer represented by the general formula (Ib) contains a repeating unit having other acid-decomposable group. Examples of such a repeating unit include an acid-decomposable group Rx in the polymer represented by the general formula (Ia).
It is preferable to represent resin of Example ③ by the following general formula (Ic).
General formula (Ⅰc)
In formula (Ic), R ₁ to R ₃ and Z have the same meaning as in formula (I) and (II), respectively. B ₂ is either an alicyclic group or a divalent alkylene group containing a divalent alicyclic group. Rx represents an acid-decomposable group, R ₁₀ ′ may be the same or different and represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms optionally substituted. The alicyclic group in B _{2 preferably} has 6 to 30 carbon atoms, and in the case of having 7 to 25 carbon atoms, it is more effective and there is a divalent group derived from the aforementioned alicyclic structure. An alkylene group consisting of a divalent group bonded to an alicyclic group is a linear or branched alkylene group having 1 to 4 carbon atoms, optionally substituted, and examples of the acid-degradable group represented by Rx include the acid-degradable groups described above. There is a flag.
Acid-degradable resins, in addition to the repeating units described above, are repeat-derived from various monomers to control not only dry-etch resistance, development of standard developing solutions, adhesion to substrates, resist profiles, but also clarity, heat resistance and sensitivity. Polymers containing units can be used.
Examples of such repeating units include, but are not limited to, those derived from the following monomers. By combining the above repeating units, in particular, (1) solubility in the composition consisting of methyl, ethyl, propyl, and isopropyl, (2) film formation characteristics (glass transition temperature), (3) alkali development, (4) resist Loss (hydrophobic / hydrophilic; selection of alkali-soluble groups) (5) adhesion to surfaces not exposed to the substrate (6) dry-etch resistance
Examples of such comonomers are compounds having an addition-polymerizable unsaturated bond selected from acyl esters, metaacyl esters, acrylamides, allyl compounds which are analogs thereof, vinyl esters and the like.
Detailed examples thereof include alkyl groups having 1 to 10 carbon atoms.
Alkyl acrylates (e.g. methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chlorooctyl acrylate, 2-hydrate Hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, perfuryl Acrylic esters such as acrylates, tetrahydropulfuryl acrylates; alkyl methacrylates with alkyl groups having from 1 to 10 carbon atoms (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl meth) Acrylate, Amyl Methacrylate, Hexyl Methacrylate Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholol propane monomethacrylate, pentaerythritol monomethacrylate, perfuryl methacrylate, tetrahydro perfuryl methacrylate) Mesacrylic esters;
Acrylamide and its analogues, N-alkylacrylamides (examples of alkyl groups, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl with 1 to 10 carbon atoms) and N, N-dialkylacrylamides (examples of each alkyl, methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl) having 1 to 10 carbon atoms, and N-hydroxyethyl-N-methylacrylamide N-2-acetamidoethyl-N-acetylacrylamide;
Mesacrylamide and its analogues are N-alkylmethacrylamides (examples of alkyl groups having 1 to 10 carbon atoms, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl), and N, N -Dialkylmethacrylamides (examples of each alkyl group, ethyl, propyl, butyl) and N-hydroxyethyl-N-methylmethacrylamide;
Allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl sterate, allyl benzoate, allyl acetoacetate, allyl lactate) and allyloxyethanol;
Alkyl vinyl ethers (e.g. hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl Vinyl ethers such as vinyl ether);
Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate, vinyl lactate Tate, vinyl Vinyl esters such as -phenyl butyrate and vinyl cyclohexyl carboxylate;
Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate); Dialkyl fumarates (eg, dibutyl fumarate) and monoalkyl fumarates; Acrylic acid, mesacrylic acid, crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, mesacrylonitrile, maleonitrile and the like.
In addition to the compounds listed above, other addition-polymerizable unsaturated compounds may be used as long as they can be copolymerized with the various repeating units described below.
In acid-degradable resins, the molar ratio of each type of repeating unit is not only the dry-etch resistance of the resist, but also the development in the standard developer, the adhesion to the substrate, the resist profile and clarity, the heat resistance, and the sensitivity to the resist. Determined appropriately for the purpose of controlling general characteristics.
The composition of the repeating units each having a group represented by the general formula (I) in the acid-degradable resin is preferably 0.005 to 40 mol% based on the total repeating monomer units, but more preferably 0.01 to 30 mol%, more preferably 0.02 It is most effective when it is 20 mol%. Since the composition of the repeating unit having a group represented by the general formula (I) is 0.005 mol% or less, it is difficult to obtain the effects of the present invention. In that regard, more than 40 mol% of components are undesirable because there is a risk of damaging the profile and increasing the film reduction rate.
When the resin is exposed to KrF for use, the composition of the repeating unit containing an acid-decomposable group in the acid-decomposable resin is preferably 3 to 65 mol% based on the total repeating monomer units, but is preferably 5 to 60 mol%. More preferably, it is most effective when it is 7-55 mol%.
In the case where the present resin is exposed to KrF for use, the composition of the repeating unit containing an acid-decomposable group in the acid-decomposable resin is illustrated below.
When acid-decomposable resins are classified as resins of the example ①, the composition of the repeating unit is preferably 20 to 70 mol% based on the total repeating monomer units, more preferably 25 to 65 mol%, more preferably 30 to 60 mol%. Is the most effective. When classifying acid-decomposable resins into resins ②, the composition of the repeating units is 10-70 mol% in terms of the total repeat monomer units (except for the Ra-containing portion is decomposed to acid), but 15-65 Mole% is more preferable, and 20 to 60 mol% is most effective. When classifying the acid-decomposable resins into the resin of Example ③, the composition of the repeating unit is preferably 20 mol% or more based on the total repeating monomer unit rule, more preferably 25 mol%, and most effective when 30 mol%. to be.
The repeating unit composition containing an alicyclic group in the acid-decomposable resin when the resin is used after exposure to ArF is illustrated below. When classifying acid-degradable resins into resins, the composition of the repeating unit is preferably 30 to 70 mol% based on the total repeating monomer units, but more preferably 35 to 65%, and 40 to 60 mol% Most effective. When classifying acid-decomposable resins into resins ②, the composition of the repeating unit is preferably 30 to 70 mol% based on the total repeating monomer units, but more preferably 35 to 65%, and 40 to 60 mol% Most effective. When classifying the acid-decomposable resins as an example ③ resin, the composition of the repeating unit is preferably 40 mol% or more based on the total repeating monomer units, but more preferably 45 mol% or more, and 50 mol% or more is most effective. .
Carbonyl, hydroxy, cyano, lactone groups and the like can be combined to impart adhesion to the acid-degradable resin exposed to ArF according to the present invention.
The acidity of the acid-decomposable resin is preferably 1.5 meq / g or less, more preferably 1.2 meq / g or less, and most effectively 1.0 meq / g.
The composition of the repeating units derived from the selective copolymers in the foregoing resins can be determined depending on the effective action of the resist. Generally, however, the composition is preferably 99 mol% or less, based on the actual repeating unit, 90 mol% or less is more preferable, and 80 mol% or less is most effective.
The molecular weight of the acid-decomposable resins described above is preferably 1,000 to 1,000,000 based on the weight-average molecular weight (M _w ; measured value of standard polystyrene). It is more preferable when it is 1,500-500,000, and it is most effective when it is 2,500-100,000. The larger the molecular weight of the resin, the better the heat resistance and other properties, while the developability or any other properties tend to decrease. The molecular weight of the resin is limited to values in the preferred range for balancing these features.
The acid-degradable resins used in the present invention can be synthesized by conventional methods (eg, radical polymerization).
In the first aspect of the present invention, the composition of the acid-decomposable resin is preferably 40 to 99.99% by weight, more preferably 50 to 99.97% by weight, based on the total solid components in the positive photoresist composition.
In another aspect of the invention, the resin used in the composition is acid decomposed to increase solubility in alkali, as described below.
In general formulas (pI) to (pVI), the alkyl group represented by R ₁₂ to R ₂₅ is a linear and branched alkyl group having 1 to 4 carbon atoms optionally substituted. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec butyl, t-butyl.
Substituents for the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine, chlorine, bromine, iodine atom), acyl group, acyloxy group, cyano, hydroxy, carbonyl, alkoxycarbonyl group, There is nitro.
The alicyclic hydrocarbon group represented by R ₁₁ to R ₂₅ and the alicyclic hydrocarbon group constituting Z having each carbon atom bonded thereto may be monocyclic or polycyclic. Examples thereof include groups having a monocyclic, bicyclic, tricyclic or tetracyclic structure having five or more carbon atoms. The alicyclic structure preferably has 6 to 30 carbon atoms, but more preferably 7 to 25 carbon atoms. In addition, an alicyclic hydrocarbon group has one or more substituents, contains an alicyclic structure therein, or consists of an alicyclic hydrocarbon group.
In the present invention, preferred examples of the alicyclic structure include admanthyl, nordemanthyl, decalin residue, tricyclodecanyl, tetracyclodecanyl, norbornyl, sedorol residue, cyclododecanyl, and more effective. Examples are adenmantyl, decalin residues, norbornyl, sedorol residues, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, cyclododecanyl.
Examples of such alicyclic hydrocarbon group substituents include alkyl groups, substituted alkyl groups, halogen atoms, hydroxy, alkoxy groups, carboxy, and alkoxycarbonyl groups, and preferred examples of alkyl groups include lower grades such as methyl, ethyl, propyl, isopropyl, and butyl. There are alkyl groups, and substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups, and alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy.
Examples of alkali-soluble groups each protected by a structure represented by any of the above-described resin formulas (pI) to (pVI) include various groups disclosed in the art. Detailed examples include carboxy, sulfo, phenol and thiol groups. Of these, carboxy and sulfo groups are good.
Preferred examples of alkali-soluble groups each protected by the structure represented by any of the above general formulas (pI) to (pVI) include groups represented by the following (pV) to (pVI).
In the said resin, the repeating unit which has alkali-soluble group each protected by the structure represented by any of general formula (pI)-(pVI) is represented by the following general formula (pA).
In formula (pA), R is the same or different and represents a linear or branched alkyl group having 1 to 4 carbon atoms, each hydrogen atom, halogen atom, optionally substituted, and A represents a single bond, alkylene group, substituted One or two or more components selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfoamide group, a urethane group, and a urea group are indicated.
R <_3> represents group represented by either of general formula (pI)-(pVI).
The detailed example of the monomer which comprises the repeating unit represented by general formula (pA) is shown below.

In addition to the repeating unit containing the alkali-soluble group protected by the structure represented by any one of (pI)-(pVI), the other repeating unit may contain the said resin.
Such optional repeating units are represented by the following general formula (AI).
In formula (AI), R is the same meaning as defined above, and B represents an acid-degradable group such as a halogen atom, a cyano group, -C (= O) -YA-Rc9 or -COORc11, wherein Y represents a divalent linking group selected from an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , -NHSO ₂ NH-, and Rc9 is -COOH, -COORc10, where Rc10 has the same meaning as Rc11. Or any of the lactone structures shown below), -CN, a hydroxy group, an optionally substituted alkoxy group, -CO-NH-Rc11, -CO-NH-SO ₂ -Rc11, Any one of the lactone structures, Rc11 represents an optionally substituted alkyl group or an optionally substituted cyclic hydrocarbon group, A represents a single component or a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, A compound selected from the group consisting of carbonyl group, ester group, amide group, sulfoamide group, urethane group, and urea group It indicates the body.
General formula [Ⅲ]
General formula [Ⅴ]
In the above formula, R _a , R _b and R _c each represent an optionally substituted hydrocarbon group, and S represents an integer of 2 or more.
The acid-degradable group is preferably a group represented by -C (= O) -X ₁ -R ₀ . R ₀ contains 1-alkoxyethyl groups such as t-butyl, t-amyl, isobornyl and 1-ethoxyethylene, 1-butoxyethylene, 1-isobutoxyethylene, 1-cyclohexylethyl, 1-methoxymethyl, Alkoxymethyl groups, such as 1-ethoxymethyl, tetrahydropyranyl, and tetrahydrofuranyl. Trialkylsilyl group and 3-oxocyclohexyl group. X ₁ is represented by an oxygen atom, a sulfur atom, -NH-, -HNSO _2- , or -NHSO ₂ HN-, but is preferably an oxygen atom.
The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, but more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Examples thereof are most effective when methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl.
Cyclic hydrocarbon groups include cycloalkyl groups, cross-linked hydrocarbons, specifically cyclopropyl, cyclopentyl. Cyclohexyl. Accidental. Carbonyl, isobonyl, tricyclodecanyl, dicyclopentenyl, norbornane-epoxy, menthyl, isomentyl, neomentyl, tetracyclododecane.
Examples of the alkoxy group include methoxy, ethoxy, prooxy, butoxy and the like having 1 to 4 carbon atoms.
Substituents for the alkyl, cycloalkyl and alkoxy groups include those containing 1 to 4 carbon atoms such as hydroxy, halogen atom, carboxy, alkoxy group, acyl group, cyano and acyloxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy, examples of the acyl group include formyl and acetyl, and examples of the acyloxy group include acetoxy.
In the general formulas (AI) and (pA), an alkylene group substituted with an alkylene group is represented by the following formula.
[C (R _a1 ) (R _b1 )] _r-
Wherein R _a1 and R _b1 are the same or different and each is a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom. A hydroxyl group and an alkoxy group are shown. The alkyl group is preferably an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, but a substituent selected from the group consisting of methyl, ethyl, propyl, isopropyl. Substituents of substituted alkyl groups include hydroxy, halogen atoms and alkoxy groups, and alkoxy groups include methoxy, ethoxy, propoxy and butoxy having 1 to 4 carbon atoms. In addition, r points out the integer of 1-10.
Halogen atoms include chlorine, bromine, fluorine and iodine.
Preferred examples of B are an acid-decomposable group and a group represented by -COOLc, wherein Lc is one of those represented by the general formulas (III) to (V) described below.
As described above, R _a , R _b, and R _C each independently represent a hydrogen atom or a hydrocarbon group. Hydrocarbon groups include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 10 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, and examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, Octyl and cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, and aralkyl groups are benzyl, phenethyl, naphthylethyl.
When R _a , R _b, and R _C are alkyl, cycloalkyl, aralkyl, these groups have one or more substituents, which include halogen atoms such as chlorine, bromine and fluorine atoms, and -CN, -OH, 1 Alkyl groups, such as benzyl and phenethyl, Trimethylsilyl and trimethoxysilyl There is a Cyril like this. It is not possible to say that substituents are necessarily limited to these examples.
In order to faithfully carry out the development of the present invention and other objects, R _a , R _b, and R _C in the general formulas [III] to [V] are each optionally selected from hydrogen atoms, having 1 to 8 carbon atoms. Although it is good also when it is a substituted alkyl group, it is more preferable when it is an optionally substituted aralkyl group which has 7-12 carbon atoms, and it is most effective when it is hydrogen atom, methyl, and ethyl each individually.
The symbol S indicating an integer of 2 to 6 may be 2 to 4, and 2 is most preferable.
In the acid-decomposable resin according to the present invention, the selective comonomer represented by general formula (AI) contains an acid-decomposable group than an alkali-soluble group protected by the structure represented by any one of general formulas (pI) to (pVI). It is good. Such acid-degradable groups in the resin are preferably groups represented by -C (= 0) -OR ₀ as described above.
In the second aspect of the present invention, the acid-decomposable groups are not only dry-etch resistance, but also develop in a standard developing solution, properties required for resist in general, such as adhesion to a substrate, resist profile and clarity, heat resistance, and sensitivity. In order to control and the like, it may be used as a copolymer containing repeating units derived from various monomers in addition to the repeating units described above.
Such repeating units are derived from the following monomers, but the monomers usable are not necessarily limited thereto.
By combining the above repeating units, in particular, (1) solubility in the composition consisting of methyl, ethyl, propyl, and isopropyl, (2) film formation characteristics (glass transition temperature), (3) alkali development, (4) resist Loss (hydrophobic / hydrophilic; selection of alkali-soluble groups) (5) adhesion to surfaces not exposed to the substrate (6) good dry-etch resistance.
Examples of comonomers include allyl compounds and addition-polymerizable compounds selected from acrylic esters, mesacryl esters, acrylamides and analogs thereof, mesacrylamides and analogs thereof. Vinyl esters, vinyl ethers, and the like, and specific examples thereof include acrylic esters such as alkyl acrylates having alkyl groups having 1 to 10 carbon atoms (eg, methyl acrylate, ethyl acrylate, amyl acrylate, cyclohexyl acrylic). Latex, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethyl Allpropane acrylate, pentaerythritol acrylate, monoacrylate, benzyl acrylate, methoxybenzyl acrylate, perfuryl acrylate, tetrahydroperfuryl acrylate);
Methacryl esters such as alkyl methacrylates with alkyl groups having from 1 to 10 carbon atoms (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, Hexyl Methacrylate, Cyclohexyl Methacrylate, Benzyl Methacrylate, Cyclobenzyl Methacrylate, Octyl Methacrylate, 2-hydroxyethyl Methacrylate, 4-hydroxybutyl Methacrylate, 5-hydroxypentyl Methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylpropane monomethacrylate, pentaerythritol methacrylate, perfuryl methacrylate, tetrahydroperfuryl methacrylate);
Acrylamide and N-alkylacrylamides (examples of alkyl groups, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, having 1 to 10 carbon atoms), N, N -Dialkylacrylamides (examples of each alkyl group, methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl) having 1 to 10 carbon atoms, N-hydroxyethyl-N-methylacrylamide, N- 2-acetamidoethyl-N-acetylacrylamide;
Analogues such as mesacrylamide and N-alkylmethacrylamides (examples of alkyl groups, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl with 1 to 10 carbon atoms), N, N-di Alkylmethacrylamides (examples of alkyl groups, ethyl, propyl, butyl), N-hydroxyethyl-N-methylmethacrylamide;
Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl sterate, allyl benzoate, allyl acetoacetate, allyl lactate);
Alkyl vinyl esters (e.g. hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl Vinyl ethers;
Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetoacetate, vinyl lactate, vinyl Vinyl esters such as -phenyl butyrate and vinyl cyclohexyl carboxylate;
Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate); Dialkyl fumarates (e.g., dibutyl fumarate); acrylic acid, mesacrylic acid, crotonic acid, itaconic acid, maleic anhydride, maleamide, acrylonitrile, mesacrylonitrile and the like.
In addition to the compounds listed above, the addition-polymerizable unsaturated compounds described above can be used as long as they can form a copolymer with the various repeating units described above.
In acid-degradable resins, the molar ratio of each type of repeating unit is not only dry-etch resistance, but also generally required for resist such as development in standard developing solution, adhesion to substrate, resist profile and clarity, thermal resistance, and sensitivity. It is determined appropriately to control the property, etc.
In the acid-degradable resin, the composition of the repeating unit containing an alkali-soluble group protected by some of the structures represented by one of general formulas (pI) to (pVI) is generally 30 to 30 based on the total repeating monomer units. It is 70 mol% and 30-65 mol% is good, but 40-60 mol% is more preferable.
The composition of the repeating unit containing an alkali-soluble group protected by some structure represented by any one of general formulas (pI) to (pVI) is generally 70 mol% or less, based on the total repeating monomer units, and 5 to 65 mol% is good, but 10-60 mol% is more preferable.
The composition of the carboxy group imparting adhesion to the resin is generally 2.0 meq / g or less and preferably 1.8 meq / g or less, but more preferably 1.5 meq / g or less.
In addition, the composition of the repeating unit derived from the optional comonomer described in the resin is appropriately determined depending on the action of the desired resist. In general, however, the composition of such optional repeating units is less than or equal to 99 mol% and less than or equal to 90 mol%, based on the total repeating monomer units, but less than or equal to 80 mol% is most effective.
Based on the weight-average molecular weight (Mw; measured by standard polystyrene), the molecular weight of the acid-decomposable resins described above is preferably 1,000 to 1,000,000, but more preferably 1,500 to 500,000, even more so when 2,000 to 200,000. For example, 2,500 to 100,000 are most effective.
The larger the molecular weight of the resin, the better the heat resistance and other properties, while the developability or any other properties tend to decrease. The molecular weight of the resin is limited to values in the preferred range for balancing these features.
Acid-degradable resins used in the present invention can be synthesized by conventional methods (e.g., radical polymerization).
In the positive photoresist composition according to the second aspect of the present invention, the composition of the acid-decomposable resin is preferably 40 to 99.9 wt% based on the total solid components in the resist composition, but more preferably 50 to 99.97 wt%.
In another aspect of the invention, the fluorine and / or silicone component surfactants contained in the positive photoresist composition are described below.
The positive photoresist composition of the present invention may contain at least one fluorine component and silicone component or both fluorine and silicon atoms as surfactants.
When the positive photoresist composition of the present invention contains the acid-decomposable resin described above in a composite bonded to at least one of the surfactants, it is exposed to a light source that emits light having a wavelength of 250 nm or less, especially a wavelength of 220 nm or less. Not only can a resist pattern with reduced development defects be obtained, scum is generated, and the resist has a line width with excellent reproducibility.
Examples of surfactants are U.S. Pat. JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432 Publication JP-A-9-5988. In particular, the following surfactants can be used commercially.
Commercially available surfactants in the present invention include F-Top EF301 and EF303 (manufactured by New Akita Chemical Co., Ltd.) FC430 and FC431 (manufactured by 3M Sumitomoto), Megapacks F171, F173, F176, F189, and R08 Chemical company), sulfone S382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and polysilonic acid polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) is also used as a silicone surfactant. Can be used.
The bonding ratio of such surfactant is generally 0.001 to 2% by weight based on the solid component in the composition of the present invention, but 0.01 to 1% is good.
These surfactants may be used alone or in combination of two or more thereof.
[1] Compounds decomposed by the action of an acid that generates sulfonic acid (hereinafter referred to as a sulfone-acid-generating compound) are used in the composition in another aspect of the present invention, which will be described below.
The compounds which generate sulfonic acids in the present invention are stable in the absence of acid, but decompose under the action of the acid generated by the photo-acid generator upon exposure to produce sulfonic acid. The acid produced due to the sulfone-acid-generating compound preferably has a high acidity. In detail, dissociation constant pKa is preferably 3 or less, but more preferably 2 or less.
Preferred examples of acids generated due to sulfone-acid-generating compounds are sulfonic acids having alkyl, cycloalkyl, aryl, aralkyl groups. Preferred examples of the sulfone-acid-generating compound include compounds represented by the following general formulas (1) to (5).
In general formula (1)-(5),
R 'represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
R ' ₀ represents a group such as -COOR' ₀ and is decomposed by the action of an acid.
R ' ₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group.
R ' ₂ represents an alkyl group or an aralkyl group.
R ' ₃ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
If R ' ₄ and R' ₅ are bonded to each other to form a ring, each independently represents an alkyl group.
R ' ₆ represents a halogen atom or an alkyl group.
R ' ₇ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
R ' ₈ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
R ' ₉ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group if R' ₉ is bonded to R ' ₇ to form a ring.
R _'10 represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group.
R _'11 is R' ₁₀ and, if forming the R 'ring ₁₁ is bonded, represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group, an alkenyl group.
The alkyl groups of formulas (1) to (5) include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and octyl.
Cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, adementyl, bonyl, isobonyl, tricyclodecanyl, dicyclopentenyl, norbornane-epoxy, menthyl, isomentyl, neomentyl, tetracyclodecanyl and Some have the same 4-10 carbon atoms.
An aryl group has 6-14 carbon atoms, such as phenyl, naphthyl and toryl.
Aralkyl groups have 7 to 20 carbon atoms, such as benzyl, phenethyl and naphthylethyl.
The alkoxy group has one to eight carbon atoms such as methoxy, ethoxy, propoxy and butoxy.
Alkenyl groups include those having 2 to 6 carbon atoms such as vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, and cyclohexenyl.
An aryloxy group has 6 to 14 carbon atoms such as phenoxy and naphthoxy.
Alkenyloxy groups have two to eight carbon atoms such as vinyloxy and allyloxy.
Substituents described above have one or more substituents. Such substituents include halogen atoms such as chlorine, bromine and fluorine, -CN, -OH, alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and acetylamino And an acylamino group such as benzyl and phenethyl, an aralkyl group such as benzyl and phenethyl, an aryloxyalkyl group such as phenoxyethyl, an alkoxycarbonyl group having 2 to 5 carbon atoms, and an acyloxy group having 2 to 5 carbon atoms. It is not limited only to the example enumerated above as a substituent.
Examples of the ring containing R ' ₄ and R' ₅ , each bonded to each other, include a 1,3-dioxolane ring and a 1,3-dioxane ring.
Examples of the ring containing R ' ₇ and R' ₉ each bonded to each other include a cyclopentyl ring and a cyclohexyl ring.
Examples of the ring containing R _'10 and R' ₁₁ each bonded to each other include a 3-oxocyclohexenyl ring and a 3-oxoindenyl ring each containing an oxygen atom.
R ' ₀ is 1-alkoxyethyl groups, such as alkyl groups, such as t-butyl, t-amyl, and isobornyl, and 1-ethoxyethyl, 1-butoxy buttyl, 1-isobutoxyethyl, and 1-cyclohexyloxylethyl And alkoxymethyl groups such as 1-methoxyethyl and 1-ethoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, trialkylsilyl groups, and 3-oxycyclohexyl groups.
R ', R' ₀ to R _'1 ~ R' Preferred example of the ₁₁ has been shown in the following.
R ': methyl, ethyl, propyl, butyl, octyl, trifluoromethyl, nonafluorobutyl, heptadecafluorooctyl, 2,2,2, -trifluorooctyl, phenyl, pentafluorophenyl, methoxy Phenyl, toluyl, mesityl, fluorophenyl, naphthyl, cyclohexyl, camphor groups.
R ' ₀ : t-butyl, methoxymethyl, ethoxymethyl, 1-ethoxyethyl, tetrahydropyranyl
R'1: methyl, ethyl, propyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, methoxy, ethoxy, propoxy, phenoxy, naphthoxy.
R'2: methyl, ethyl, propyl, butyl, benzyl.
R ' ₃ : methyl, ethyl, propyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, naphthylmethyl.
R ' ₄ , R' ₅ : methyl, ethyl, propyl; Ethylene, propylene when R ' ₄ and R' ₅ are bonded to one another;
R ' ₆ : halogen atom, methyl, ethyl.
R ' ₇ , R' ₉ : halogen atom, methyl, ethyl, propyl, butyl, pentyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl; Examples of the ring containing R ' ₇ and R' ₉ bonded to each other are cyclopentyl, cyclohexyl.
R _'10 : methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, phenyl, naphthyl, benzyl, phenoxy, naphthoxy, vinyloxy, methyl vinyloxy, R inde-oxo-3-cyclohexenyl, 3-oxo optionally containing oxygen is _'10 and R' ₁₁ combine with each other carbonyl.
R _'11 : methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, phenyl, naphthyl, benzyl, phenoxy, naphthoxy, vinyl, allyl; Examples of rings which combine with each other to contain R ′ ₁₁ and R ′ ₁₀ include 3-oxocyclohexenyl, 3-oxoandenyl.
Specific examples of the compound represented by General Formulas (1) to (5) are shown below. However, the composition of the present invention is not limited to these examples.

Particularly effective examples of the sulfone-acid-generating compound used in the present invention are compounds represented by the general formula (4).
The amount of the sulfone-acid-generating compound added to the composition of the present invention is preferably 0.01 to 10% by weight based on the total solid component of the composition, but is preferably 0.05 to 5% by weight.
[2] The compounds which generate acid when irradiated with actinic radiation and radiation (photo-acid generator) which can be used in the first and second embodiments of the present invention are described below.
The photo-acid generator used in the present invention is a compound that generates an acid upon actinic radiation and irradiation.
Examples of the compounds used in the present invention that decompose or generate acids upon irradiation of actinic radiation and radiation are used in photoinitiators in cationic photopolymerization, photoinitiators in radical polymerization, photobleachers in salt coloring, optical color converters, and microresists. Known light (e.g. ultraviolet light having a wavelength of 400-200 nm, in particular g-ray, h-ray, i-ray, KrF excimer laser light) and ArF excimer laser light, electron beam, X-ray, molecular beam, There are compounds that generate an acid by the action of an ion beam. Such photo-acid generators are suitably used alone or in mixture of two or more.
Compounds used in the present invention that generate acids upon irradiation with actinic radiation and radiation include the following onium salts: S.I. Scringer, PHOTOGR. SCI. UK., 1, 387 (1974) and T.S. Et al., Polymers, diazonium described in 21, 423 (1980); Ammonium salts described in US Pat. No. 4,069,055 and US Reissue Pat. No. 27,992, JP-A-3-14-.140; D.C. Necker et al., Macromolecules, 17, 2468 (1984), C.S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo, October. (1988), phosphonium salts described in US Pat. No. 4,609,056; J.V. Crivelo et al., Macromolecules, 10 (6), 1307 (1977), Chem & Eng. News, November 28, p. 31 (1988), European Patent 104,143, and Iodonium Salts described in US Patent 339,049 410,201, JP-A-2-150,848, JP-A-2-296,514; J.V. Krivelo et al., Polymer J., 17, 73 (1985), J.V. Krivelo et al., J. Org. Chem., 43, 3055 (1978), W. R. Watt et al., J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J.V. Cribellow et al., Polymer Bull., 14, 279 (1985), J.V. Krivelo et al., Macromolecules, 14 (5), 1141 (1981), J.V. Krivelo et al., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patents 370,693, 161,811, 410,201, 339,049, 233, 567, 297,443, 297,442, US Patents 3,902,114, 4,933,377, 4,760,013, 4,734,444, 2,833,827, Todo Patent 2,904,626, 3604, 604, 604,3604 Sulfonium salts described in A-7-28237 and JP-A-8-27102; J.V. Krivelo et al., Macromolecules, 10 (6), 1307 (1977) and J.V. Krivelo et al., J. Polymer Sci., Polymer Chem. Ed. Selenium, described in 17, 1047 (1979); C.S. Wen et al., Teh, Proc. Conf. Rad. Asonium salts described in Curing ASIA, p 478 Tokyo, October. (1988); In that regard, in detail, U.S. Patent No. 3,905,815, JP-B-46-4605 ("JP-B" here means "examined Japanese patent edition"), JP-A-48-36281, JP-A-55-32070, JP-A-60-236736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, Organic halogen compounds described in JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339; K. Mayer et al., J. Rad. Curing, 13 (4), 26 (1986), T.P. Gil et al., Inorg. Chem., 19, 3007 (1980), D. Ostruck, Acc. Chem. Organic metal compounds / organic halide compounds described in Res., 19 (12), 377 (1896), JP-A-2-161445; S. Hayase et al. Polymer Sci., 25, 753 (1987), E. Lakemanis et al., J. Polymer Sci., 25, Polymer Chem. Ed., 23, 1 (1985), QQZhu et al., J. Photo Chem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24) 2205 (1973 ), DHR Barton et al., J. Chem. Soc., 3571 (1965), P. M. Collins et al., J. Chem. Soc., Perkin I, 1965 (1975), M. Rubinstein et al., Tetrahedron Lett, (17), 1445 (1975), J.W. Walker et al.,, J. Am. Chem. Soc. 110, 7170 (1988), S.C. Busman et al., J. Imaging Technol., 11 (4), 191 (1985), H.M. Hollyhan et al., Macromolecules, 21, 2001 (1988), P.M. Collins et al., J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al., Macromolecules, 18, 1799 (1985), E. Lakeman et al.,, J. Electrochem. Soc., SolidState Sci. Technol., 130 (6), F.M. Holley et al., Macromolecules, 21, 2001 (1988), European Patents 0, 290, 750, 046, 083, 156, 535, 271, 851 and 0,388, 343, US Patents 3,109,710 and 4,181,531, JP-A-60 Photo-acid generators having an O-nitrobenzyl type protecting group described in 198538, JP-A-53-133022; M. Tunoka et al., Polymer Preprints, Japan, 35 (8), G. Burner et al., J. Rad. Curing, 13 (4), WJ Mizus et al., Coating Techol., 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan, 37 (3), European Patent 0, 199, 672, 84, 515, 044, 115, 618, 564 and 0, 101, 122, US Patents 4,371,605 and 4,431,774, JP-A-64-18143, JP-A-2-245756 and JP- A compound represented by the iminosulfonate described in A-3-140109 and photodegraded to generate sulfonic acid. Disulfone compounds described in JP-A-61-166544 and JP-A-2-71270; The dazoketosulfone and diazodisulfone compounds described in JP-A-3-103854, JP-A-3-103856, and JP-A-4-210960.
Moreover, the compound obtained by combining the compound and group which generate | occur | produce an acid by the action of light to the main or sub chain of a polymer can also be used.
Examples of such polymeric compounds are described in M.E. Woodhouse et al., J. Am. Chem. Soc., 104, 5586 (1982), S.P. Papas et al., J. Imaging Sci. 30 (5), 218 (1986), S. Condo et al., Macromole. Chem., Rapid Commun., 9, 625 (1988), Y. Yashun et al., Macromol. Chem., 152, 153, 163 (1972), J.V. Krivelo et al., J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), US Pat. No. 3,849,137, German Patent 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP- A-63-146038, JP-A-63-163452, JP-A-62-153853, and JP-A-63-146029.
In addition, usable compounds which generate acids due to the action of light are described in V.N.R. Filey, Synthesis, (1), 1 (1980), A. Abad et al., Tetrahedron Lett., (47) 4555 (1971), D.H.R. Baron et al., J. Chem. Soc., (C), 329 (1970), US Patent 3,779,778, and European Patent 126, 712.
Among the compounds which generate an acid upon irradiation with actinic radiation and radiation listed above, compounds which are particularly effective are described below.
(1) The trihalomethyl-substituted oxazole derivative represented by the following general formula (PAG1), and the trihalomethyl-substituted-triazine derivative represented by the following general formula (PAG2).
In the above formula, R ²⁰¹ represents a substituted or unsubstituted aryl or alkenyl group .; R ²⁰² represents a substituted or unsubstituted aryl, alkenyl, alkyl group; Y represents a chlorine and bromine atom.
Although a more detailed example is given below about the above, the compound represented by general formula (PAG1) or (PAG2) is not necessarily limited to this.

(2) The iodonium salt is represented by the following general formula (PAG3), and the sulfonium salt is represented by the general formula (PAG4).
In the above formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Examples of preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, hydroxy groups, mercaptos and halogen atoms.
R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl or aryl group, and an aryl group having 6 to 14 carbon atoms and an alkyl group having 1 to 8 carbon atoms and a substituted derivative thereof are preferable. Preferred substituents of the aryl group are alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro, carboxy, hydroxy and halogen atoms.
Preferred substituents of the alkyl group include an alkoxy group, carboxy and alkoxycarbonyl group having 1 to 8 carbon atoms.
Z ⁻ represents a counter anion. Examples thereof include molten aromatic sulfonate anions and sulfonate groups such as perfluoroalkanesulfonate anion, pentafluorobenzenesulfonate anion, naphthalene-1-sulfonate anion, and untraquinonesulfonate anion. There is a dye. Specific examples ^{_{include, BF -, AsF 6 -,}} PF 6 -, SbF 6 - a ^{_{-, SiF 6 2-, ClO 4}} -, CF 3 SO 3. However, Z ⁻ is not necessarily limited to this example.
R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ may be bonded to each other through a single bond or a substituent thereof. Ar ¹ and Ar ² may be bonded to each other in a similar manner.
The compounds represented by the formulas (PAG3) and (PAG4) will be given below, but are not necessarily limited to those illustrated.



Onium salts represented by the formulas (PAG3) and (PAG4) are known. For example, they are J.W. Knapzuki et al., J. Am. Chem. Soc., 91, 145 (1969), A. L. Maycock et al., J. Org. Chem., 35, 2532 (1970), E. Coetas et al., Bull. Soc. Chem. Belg., 73, 546 (1964), H. M. Leicester, J. Ame. Chem. Soc., 51, 3587 (1929), J.V. Cribelo et al., J. Polymer. Chem. Ed., 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473 and JP-A-53-101331.
(3) The disulfone derivative is represented by the following general formula (PAG5), and the iminosulfonate derivative is represented by the following general formula (PAG6).
In the above formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group; R ²⁰⁶ represents a substituted or unsubstituted alkyl or aryl group; A represents a substituted or unsubstituted alkylene, alkenylene, arylene group.
Although the detailed example about this is given, the compound represented by general formula (PAG5) or (PAG6) is not necessarily limited to this.

In the first aspect of the present invention, the amount of addition of such a compound that is generated by decomposing an acid upon irradiation with actinic radiation and radiation to the photoresist composition is based on the total amount of the resist composition (excluding solvents). Although generally 0.001 to 20% by weight, 0.01 to 10% by weight is good, more preferably 0.1 to 5% by weight.
When the amount of these compounds decomposed and generated when irradiated with actinic radiation and radiation is 0.001% by weight or less, the result is low sensitivity. On the other hand, the addition amount of more than 40% by weight, the resist shows a very strong light absorbency, resulting in damage to the profile and narrow margins in the process (especially during high temperature drying) is unsuitable.
In the resist compositions according to the first and second aspects of the present invention, the amount of such compounds that are decomposed and generated upon irradiation of actinic radiation and radiation is based on the total amount of the resist composition (excluding solvents). It is generally 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. When the amount of these compounds decomposed and generated when irradiated with actinic radiation and radiation is 0.001% by weight or less, the result is low sensitivity. On the other hand, the addition amount of more than 40% by weight, the resist shows a very strong light absorbency, resulting in damage to the profile and narrow margins in the process (especially during high temperature drying) is unsuitable.
The positive photoresist composition of the present invention optionally contains more other components such as acid-degradable dissolution inhibiting compounds, dyes, plasticizers, surfactants, photosensitizers, organic base compounds, compounds accelerating dissolution in the developer, and the like. You may.
When applied to a substrate, the positive resist composition of the present invention is used in the form of a solution by dissolving the components described above in a solvent. Preferred examples of the solvent include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene. Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N Methylpyrrolidone, tetrahydrofuran. Such solvents may be used alone or in admixture of two or more.
More preferred examples of such solvents include 2-heptanone, -Butyrolactone, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ether ethoxypropio Nate, N-methylpyrrolidone, tetrahydrofuran.
Surfactants may also be added to the solvent. Such surfactants include nonionic surfactants, examples of which are as follows. Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, polyoxyethylene oryl ether; polyoxyethylene octylphenol ether, polyoxoethylene nonylphenol ether, poly Polyoxyethylene alkyllauryl ethers such as oxoethylene / polyoxopropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monosterate, sorbitan monooleate, sorbitan trioleate Sorbitan / fatty acid esters such as sorbitan tristerate, and the like; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monosterate, polyoxyethylene sorbitan triol Same as latex, polyoxyethylene sorbitan tristerate Poly a polyoxyethylene sorbitan / fatty acid esters. In addition, the fluorine-based surfactants include F-Top EF301, EF303, EF352 (manufactured by New Akita Chemical Co., Ltd.), Mega Pack F171, F173 (manufactured by Dainippon Ink & Chemical Co., Ltd.), fluoride FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Sulfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and organosilosane polymer KP431 (manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic or mesacryl polymer polyflow 75 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the surfactant is generally 2 parts by weight or less based on 100 parts by weight of the solid component of each resist composition of the present invention, but 1 part by weight or less is preferable.
Such surfactants are added alone or in combination of two or more.
The positive photoresist composition of the present invention described above is applied to a substrate to form a thin film. The thickness of this coated film is preferably 0.4 to 1.5 mu m.
In the production of precision integrated-circuit components (eg, silicon / silicon dioxide coating), an effective resist pattern can be obtained by applying the respective resist composition described above to a substrate using a suitable application method. Examples of such application methods include spinners or coaters that expose the applicator to light through a given mask, followed by high temperature drying and developing the applicator. Exposed light having a wavelength of 150 nm to 250 nm is preferable. Specific examples include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm), and X-rays and electron beams.
80-180 degreeC of drying temperature is good at the time of high temperature drying after exposure, It is more preferable that it is 85-160 degreeC, and 90-150 degreeC is the most effective.
As a developing solution, an aqueous alkaline solution is used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, inorganic alkalis such as sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethyl amine and n-propyl amine, diethylamine Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine, alcoholamines such as dimethylethanolamine, triethanolamine, 4 such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Quaternary ammonium salts, pyrrole, cyclic amines such as piperidine, and the like.
Alkaline aqueous solution used as a developer contains alcohol or surfactant.
The invention is described in more detail below as a reference example, but the invention is not necessarily limited to this example.
Synthesis of Photo-acid Generator (PAG 4-35)
50 g of diphenyl sulfoxide was dissolved in 80 ml of mesitylene, and 200 g of ammonium chloride was added thereto. Then, the mixture was stirred at 80 ° C. for 24 hours. After the reaction was completed, the reacted mixture was slowly poured into 2 L of ice water, and 400 ml of concentrated hydrochloric acid was added thereto. After heating the mixture at 70 ° C. for 10 minutes, the resulting reaction mixture was cooled to room temperature, washed with ethyl acetate and then purified. A solution in which 200 g of ammonium iodine was dissolved in 400 ml of distilled water was added to the purified product. The precipitated particles were removed by purification, washed with water and ethyl acetate and dried to obtain 72 g of sulfonium iodide.
50 g of the sulfonium iodide obtained above was dissolved in 300 ml of methanol. To this, 31 g of silver iodide was added, and the mixture was stirred for 4 hours. The resulting reaction mixture was purified and salt exchanged with heptadecafluorosulfonate to afford 40 g of the target compound.
Synthesis of Monomers
(1) Synthesis of Monomer (1)
100 ml of 1,3-dioxane was dissolved in 121 g of 1-methoxy-2-propanol and 182 g of styrenesulfonyl chloride.
142 g of pyridine was added thereto and cooled in an ice bath for at least 2 hours.
After the addition was terminated, the ice bath was removed and the reaction mixture was stirred for 6 hours. 2 L of ice water was poured into the resulting reaction mixture to crystallize and then extracted with ethyl acetate. The solvent was distilled off under reduced pressure, and the resulting oily residue was purified by silica gel top chromatography to obtain 103 g of a target compound as a monomer.
(2) Synthesis of Monomer (2)
Tetrahydropyrano was carried out in the same manner as in Synthesis Example (1) except that 1-methoxy-2-propanol was used, to synthesize monomer (2).
(3) Synthesis of Monomer (5)
A monomer (5) was synthesized in the same manner as in Synthesis Example (1) except that methanol was used instead of 1-methoxy-2-propanol.
(4) Synthesis of Monomer (15)
A monomer (15) was prepared in the same manner as in Synthesis Example (1) except that sulfonyl chloride such as 2-acrylamido-2-methylpropanesulphonic acid (AMPS) was used in place of styrenesulfonyl chloride. Synthesized.
(5) Synthesis of Monomer (20)
Monomer (20) was carried out in the same manner as in Synthesis Example (1) except that AMPS and 2-phenyl-2,2-dimethylethanol were used in place of styrenesulfonyl chloride and 1-methoxy-2-propanol, respectively. Synthesized.
(6) Synthesis of Monomer (21)
A monomer (21) was synthesized in the same manner as in Synthesis Example (1) except that a chloride acid such as 3-sulfopropyl methacrylate was used in place of styrenesulfonyl chloride.
(7) Synthesis of Monomer (24)
A monomer (24) was synthesized in the same manner as in Synthesis Example (6) except that cyclohexanol was used instead of 1-methoxy-2-propanol.
(8) Synthesis of Monomer (28)
A monomer (28) was synthesized in the same manner as in Synthesis Example (6) except that neopentyl alcohol was used instead of 1-methoxy-2-propanol.
(9) Synthesis of Monomer (29)
A monomer (29) was synthesized in the same manner as in Synthesis Example (6) except that 2-pentyl-2,2-dimethylethanol was used instead of 1-methoxy-2-propanol.
(10) Synthesis of Monomer (30)
A monomer (30) was synthesized in the same manner as in Synthesis Example (6) except that 2-chlorohexanol was used instead of 1-methoxy-2-propanol.
(11) Synthesis of Monomer (13)
8.5 g of sodium chloride was dispersed in 100 ml of THF. Dispersion was performed during cooling at 0 ° C, and 32 g of t-butyl acetoacetate was added dropwise over 1 hour under nitrogen vapor. After the addition was complete, the mixture was stirred for 30 minutes, and then 40 g of methyl iodide was added dropwise over 1 hour. After the reaction was completed, 100 ml of sodium bicarbonate aqueous solution was added dropwise to the reaction mixture, and the reaction mixture was stirred for 1 hour, and extracted with ethyl acetate. The ethyl acetate layer was concentrated to give t-butyl-2-methylacetoacetate.
The t-butyl-2-methylacetoacetate obtained above was dispersed in 37% aqueous formaldehyde solution and 30 g of 1,3-dioxane mixture as it was. Under nitrogen atmosphere, the resulting mixture was cooled to 10 ° C. and 14 g of potassium carbonate was added at 4 ratios. The mixture was stirred for 5 hours while maintaining the reaction temperature of 10-20 ° C., and after the reaction was completed, the reaction mixture was extracted with ethyl acetate / water. The reaction product obtained by concentrating the ethyl acetate layer was purified by silica gel top chromatography to obtain 27 g of t-butyl-2-hydromethyl-2-methylacetoacetate.
1,3-dioxolane was dissolved in t-butyl-2-hydromethyl-2-methylacetoacetate and 11 g of pyridine. The solution was cooled to 0 ° C. under a nitrogen atmosphere, and 15 g of styrenesulfonyl chloride was added dropwise over 30 minutes. After the reaction was completed, the reaction mixture was stirred for 10 hours and extracted with ethyl acetate. The obtained reaction product was purified by silica gel top chromatography to obtain 13 g of monomer (13) as a target compound.
(12) Synthesis of Monomer (31)
The t-butyl-2-hydro methyl-2-methylacetoacetate obtained in the synthesis of the above monomer (13) was substituted with 3-chlorosulfopropyl methacrylate in place of styrenesulfonyl chloride. It was used also for the synthesis of the monomer (31) in the same manner as).
(13) Synthesis of Monomer (37)
1-phenyl-1-cyclohexene was oxidized with osmium oxide in a conventional manner to obtain 1-phenyl-1,2-cis-dihydrooxycyclohexene. This 1-1-phenyl-1,2-cis-dihydrooxycyclohexene was then dissolved in 1.2 equivalents of pyridine. The solution was cooled in an ice bath at 0 ° C, and 1.1 equivalents of styrenesulfonyl chloride was added dropwise over 30 minutes. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The reaction product obtained by concentrating the ethyl acetate layer was purified by silica gel top chromatography to obtain monomer (37) as a target compound.
(14) Synthesis of Monomer (39)
1-methyl-1-cyclohexene was oxidized with osmium oxide in a conventional manner to obtain 1-methyl-1,2-cis-dihydroxycyclohexene. This 1-methyl-1,2-cis-dihydroxycyclohexene was dissolved in 1.2 equivalents of pyridine. The solution was cooled in an ice bath at 0 ° C, and 1.1 equivalents of 3-chlorosulfonyl methacrylate was added dropwise over 30 minutes. After the reaction was completed, the reaction mixture was stirred for 15 hours at a reaction temperature of 0 to 10 DEG C, and after the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The reaction product obtained by concentrating the ethyl acetate layer was purified by silica gel top chromatography to obtain monomer (39) as a target compound.
(Resin Synthesis 1)
(1) Synthesis of Resin shown above
t-butoxystyrene and the monomer described above were injected into the vessel at a ratio of 15/1. The monomer mixture was dissolved in N, N-dimethylacetamide / tetrahydrofuran = 2/8 mixed with a solvent, and 100 ml of a solution of 20% at a solid concentration was prepared. To this solution was added V-65, a Wako Pure Chemical Company company, in an amount of 1 mol%. Under a nitrogen atmosphere, this mixture was added dropwise to 10 ml of tetrahydrofuran heated to 60 ° C. over 2 hours. After the addition was completed, the reaction mixture was stirred and heated for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 3 L of methanol was poured to crystallize. The precipitated white particles were recovered.
Then, the obtained white particles were hydrolyzed under acidity to remove the portion protected by the t-butoxy group, thereby obtaining Resin (VII) as a target compound. ¹³ C NMR spectroscopy showed that this polymer had a monomer unit ratio of 25/69/6. The weight-average molecular weight of this polymer was 8,100 as measured based on GPC and standard polystyrene.
(2) Synthesis of Resins (ii) to (iii)
The monomer unit ratios and weight-average molecular weights of the resins (ii) to (iii) are shown in Table 1 below, which were synthesized by the same procedure as the synthesis of the resin (iii). In the table, the repeating units 1 to 3 of each resin correspond to the repeating units on the left and the center and on the right, but this is in the examples of the resins represented by the structural formulas described above except for the units represented by the general formula (I). Corresponding.
SuzyCharacteristics of repeat units (mol%)Weight-average molecular weight General formula (Ⅰ)Repeat unit 1Repeat unit 2Repeat unit 3 (Ii)62470 8700 (Ⅲ)72271 9600 (Ⅳ)42472 8200 (Ⅴ)52174 8400 (Ⅵ)81973 7500 (Ⅶ)92051208300 (Ⅷ)82270 8100 (Ⅸ)101872 7600 (Ⅹ)41977 8400 (Ⅹⅰ)82468 7700 (Iii)92566 7600 (Ⅹⅲ)76132 7100 (Ⅹⅳ)82255158600 (Ⅹⅴ)61020645900 (Ⅹⅵ)97021 10900 (Ⅹⅶ)62569 8700 (Ⅹⅷ)56020158900 (Ⅹⅸ)72172 9200 (Ⅹⅹ)86725 9100 (Ⅹⅹⅰ)42472 8400 (Iii)32176 9400 (Ⅹⅹⅲ)22573 8300 (Ⅹⅹⅳ)52174 8700 (Ⅹⅹⅴ)52362108500 (Ⅹⅹⅵ)32077 8800 (Ⅹⅹⅶ)42551208900 (Ⅹⅹⅷ)36730 11400
(Resin Synthesis 2)
(1) Synthesis of Resin (I)
1-Adecanthyl acrylate, 3-oxocyclohexyl mesacrylate and the monomer (21) described above were injected into the vessel at a ratio of 48/47/5. The monomer mixture was dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5 mixed with a solvent, and 100 ml of a solution having 20% at a solid concentration was prepared. To this solution, V-65, a Wako Pure Chemical Company, was added in an amount of 3 mol% and 6 mol%, respectively. Under a nitrogen atmosphere, this mixture was added dropwise to 10 ml of tetrahydrofuran heated to 60 ° C. over 3 hours. After the addition was completed, the reaction mixture was stirred and heated for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 3 L of methanol was poured to crystallize. The precipitated white particles were recovered.
¹³ C NMR spectroscopy showed that Resin (I) had a monomer unit ratio of 48/47/5. The weight-average molecular weight of this polymer was 8,600 as measured based on GPC and standard polystyrene.
(3) Synthesis of Resin (II) to (XVI)
The monomer unit ratios and weight-average molecular weights of the resins (II) to (XVI) are shown in Table 2 below, which were synthesized by the same procedure as the synthesis of the resin (I). In the table, repeating units 1 to 2 of each resin correspond to repeating units on the left and right sides, but this corresponds to resins represented by the following structural formulas, except for the units represented by the general formula (I).

SuzyRate of repeat units (mol%)Weight-average molecular weight General formula (Ⅰ)Repeat unit 1Repeat unit 2 (Ⅱ)849437300 (Ⅲ)648467200 (Ⅳ)750437700 (Ⅴ)449476800 (Ⅵ)548476900 (Ⅶ)642529400 (Ⅷ)5415410100 (Ⅸ)4524410700 (Ⅹ)548479600 (ⅩⅠ)647478100 (XII)247517200 (XIII)248507600 (XIV)353447400 (ⅩⅤ)3425510500 (ⅩⅥ)343549900
Examples 1-28 and Comparative Example 1
Preparation and Evaluation of Photosensitive Compositions
To 2 g of each resin given in Tables 3-4, 0.04 g of the photo-acid generator (PGA 3-1) described above and 0.02 g of 4-dimethylaminopyridine were added. Each mixture was dissolved in 9.5 g of propylene glycol monomethyl ether acetate and the resulting solution was filtered through a 0.2-μm spacing filter. As a result, a positive resist composition could be manufactured.
SuzyDefocusing latitude depends on line pitchSensitivity Example 1Ⅰ1.0 μm1.0 Example 2Ii1.0 μm0.8 Example 3Ⅲ1.1 μm0.6 Example 4Ⅳ1.0 μm0.7 Example 5Ⅴ1.0 μm0.8 Example 6Ⅵ1.0 μm0.9 Example 7Ⅶ1.1 μm0.7 Example 8Ⅷ1.1 μm0.7 Example 9Ⅸ1.0 μm1.0 Example 10Ⅹ1.0 μm1.0 Example 10Ⅹⅰ0.9 μm1.1
SuzyDefocusing latitude that depends on line pitchSensitivity Example 12Xii0.9 μm1.1 Example 13Ⅹⅲ0.9 μm1.0 Example 14Ⅹⅳ1.0 μm0.9 Example 15Ⅹⅴ0.9 μm1.0 Example 16Ⅹⅵ1.1 μm0.8 Example 17Ⅹⅶ1.0 μm0.9 Example 18Ⅹⅷ0.9 μm0.9 Example 19Ⅹⅸ1.0 μm0.7 Example 20Ⅹⅹ1.0 μm0.7 Example 21Ⅹⅹⅰ1.0 μm0.9 Example 22Xii1.1 μm0.7 Example 23Ⅹⅹⅲ1.0 μm0.7 Example 24Ⅹⅹⅳ1.0 μm0.7 Example 25Ⅹⅹⅴ1.1 μm0.7 Example 26Ⅹⅹⅵ1.0 μm0.8 Example 27Ⅹⅹⅶ1.0 μm0.8 Example 28Ⅹⅹⅷ1.1 μm0.8 Comparative Example 1R10.5 μm2.5
Evaluation test
Each of these resist compositions were used as spin-treated silicon flakes, and the coating was dried at 90 ° C. for 90 seconds with a vacuum suction hot-plate to obtain a 0.83 μm thick resist film.
These resist films were exposed to light using a 248-nm KrF excimer laser stepper (NA = 0.42), and immediately after exposure, each resist film was heated with a 110 ° C. vacuum suction hot-plate for 60 seconds to give a 2.38% concentration. Was immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds. After that, it was rinsed in water for 30 seconds and then dried. A test was conducted on the profile of the resist pattern obtained on the silicon flakes.
Defocus latitude, sensitivity, and development residues depending on the line pitch were evaluated with this resist pattern as follows.
Defocusing latitude depends on line pitch
Line-space patterns (patterns with densely distributed lines) and isolated-line patterns (patterns with lightly dispersed lines) each have a line width of 0.25 μm, and their defocusing latitudes The overlapping range was determined to be about 0.25 μm ± 10%. In larger ranges, the out of focus latitude that depends on the line pitch is further improved.
Sensitivity
Sensitivity is expressed as the exposure amount required for reproducing a pattern having a line width of 0.25 탆, and given as a relative value when the sensitivity value of Example 1 is 1.
The results of the evaluation are given in Tables 3 and 4.
In Comparative Example 1, a positive resist composition was prepared and evaluated in the same manner as in Example 1. Resin R <_1> is resin as described above which does not contain the repeating unit which has group represented by General formula (I), and this positive photoresist composition has a monomer unit ratio and weight of 21: 79-- The average molecular weight is 8,800, which was synthesized in the same manner as the resin.
From the results given in Tables 3 and 4, the resist composition of the comparative example was insufficient in terms of both defocusing latitude and sensitivity depending on the line pitch. In contrast, the positive photoresist composition of the present invention was at a satisfactory level in each of these actions. In addition, patterns formed during the evaluation of defocused latitude depending on the line pitch could be examined when scanning the developing residue with an electron microscope. As a result, the developing residue was observed in the pattern formed from the composition of the comparative example. In each of the patterns formed from the positive photoresist composition of the present invention, there was no development residue at all. Thus, the composition of the present invention can be said to be suitable for lithography using far ultraviolet rays such as KrF excimer laser light.
Examples 29-44 and Comparative Example 2
Add 0.18 g of photo-acid generator and 10 mg of 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) to 1.4 g of each resin in Table 5 synthesized in the synthesis examples given above. did. Each mixture was dissolved in propylene glycol monoethyl ether having a solid concentration of 14% by weight. This solution is purified with a 0.1-μm microfilter to prepare the positive resist composition of Examples 29-44.
Except for the following resin R2 used with the photo-acid generator, in Comparative Example 2, the positive resist composition was prepared in the same manner as in Examples 29-44.
Resin R2
Resin R2 was synthesized according to the methods described in JP-A-9-90637, page 18, and Example 13. Therefore, the (±) -mevalonolactone methacrylate / 2-methyl-2-ademantyl methacrylate polymer was synthesized by the following method.
In a sufficiently dry, 100-ml eggplant flask with a Teflon ^™ -coated stirrer, 4.96 g (25 mmol) of (±) -mevaronolactone, 5.89 g (25 mmol) of 2-methyl-2-edemanyl methyl 0 acrylate, 16.7 ml dioxane and 1.23 g of azobisisobutyronitrile (AIBN) were injected. The contents were stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. The reaction mixture was titrated with tetrahydrofuran (THF), and 1 liter of methanol containing a trace amount of hydroquinone was added dropwise. The resulting precipitate was purified by a glass filter, removed, and dried at 0.1 mmHg at 45 ° C. for 16 hours. The obtained white powder was dissolved in THF, and the same precipitation / drying process described above was repeatedly performed twice to obtain a white powder as a target copolymer. Yield = 7.44 g (68.7%). The obtained copolymer had a lactone / adamantyl copolymerization ratio of 46.5 / 53.5, a weight-average molecular weight (calculated based on standard polystyrene) of 14,000, and a dispersity of 2.0.
SuzyPhoto-acid generatorDefocusing latitude that depends on line pitchSensitivity Example 29IPAG-10.8 μm1.0 Example 30ⅡPAG-20.8 μm1.0 Example 31ⅢPAG-11.1 μm0.9 Example 32ⅣPAG-11.1 μm0.7 Example 33ⅤPAG-11.2 μm0.9 Example 34ⅥPAG-11.2 μm0.6 Example 35ⅦPAG-20.9 μm0.9 Example 36ⅧPAG-20.9 μm0.8 Example 37ⅨPAG-20.9 μm0.9 Example 38ⅩPAG-10.9 μm0.8 Example 39ⅩⅠPAG-11.1 μm0.7 Example 40XIIPAG-10.8 μm1.0 Example 41ⅩⅢPAG-21.1 μm0.7 Example 42ⅩⅣPAG-11.2 μm0.9 Example 43ⅩⅤPAG-10.9 μm0.8 Example 44ⅩⅥPAG-20.9 μm0.8 Comparative Example 2R2PAG-10.2 μm2.3
In Table 5, PAG-1 represents triphenylsulfonium triflate and PAG-2 represents (PAG 4-35) synthesized above.
Evaluation test
Each obtained positive photoresist composition was applied to a silicon flake of a spin applicator, and the coating was dried at 130 ° C. for 90 seconds to form a 0.5 μm thick positive photoresist film. This resist film was exposed to ArF excimer laser light (exposed using a stepper having a wavelength of 193 nm and a NA of 0.55), and the resist film was heated at 130 ° C. for 90 seconds, followed by a 2.38% concentration of tetra hydroxide. It was developed with aqueous methylammonium solution. Then, it was rinsed with distilled water to obtain a resist pattern profile.
This resist pattern was evaluated for defocus latitude and sensitivity depending on the line pitch in the following manner.
Defocusing latitude dependent on line pitch
Line-space patterns (patterns with densely distributed lines) and isolated-line patterns (patterns with lightly dispersed lines) each have a line width of 0.22 μm, and their defocusing latitudes The overlapping range was determined to be about 0.22 μm ± 10%. Larger range results in better out of focus latitude that depends on line pitch
Sensitivity
Sensitivity is expressed as the exposure amount required for reproducing a pattern having a line width of 0.22 탆, and given as a relative value when the sensitivity value of Example 29 is 1.
In view of the results given in Table 5, the positive photoresist composition of the present invention was at a satisfactory level in each of these actions. In addition, patterns formed during the evaluation of defocused latitude depending on the line pitch could be examined when scanning the developing residue with an electron microscope. As a result, the developing residue was observed in the pattern formed from the composition of the comparative example. Each pattern formed from the positive photoresist composition of the present invention did not have any development residues. Thus, the composition of the present invention can be said to be suitable for lithography using far ultraviolet rays such as KrF excimer laser light.
As demonstrated above, the present invention provides a positive photoresist composition that is excellent in defocus latitude and sensitivity depending on the line pitch, and has no development residues.
The invention is described in more detail in the following reference examples, but it should not be said that the invention is limited to this example.
Synthesis of Resin (1)
2-Butyl-2-ademaletyl methacrylate and mevalonolactone methacrylate were injected into the vessel at a ratio of 45/55. The monomer mixture was dissolved in tetrahydrofuran and 100 ml of a solution having a solid concentration of 20% was prepared. To this solution, mercapoethanol was added in amounts of 2 mol% and 4 mol%, respectively, with V-65 (manufactured by Wako Pure Chemical Company). Under a nitrogen atmosphere, this mixture was added dropwise to 10 ml of tetrahydrofuran heated at 60 ° C. over 2 hours. After the addition was complete, the reaction mixture was heated with stirring for 6 hours. Then, the reaction mixture was cooled to room temperature, and 3 L of methanol was poured to crystallize, and the precipitated white particles were recovered.
^{Through 13} C NMR spectroscopy, it was found that the obtained resin (1) had a monomer ratio of 46/54. The weight-average molecular weight of the polymer was 9,800 based on standard polystyrene as measured by GPC.
Other resins were also synthesized in this manner.
Synthesis of Resin (2)-(7)
The resins of (2) to (7) had the following structures and the monomer unit molar ratios and weight-average molecular weights given in Table 6 below, and these resins were synthesized in the same manner as in Resin (1).
SuzyAlicyclic monomer (mol%)Acid-degradable monomer (mol%)Carboxylic Acid Monomer (mol%)Molecular Weight (2)45431210300 (3)4342159600 (4)43431411200 (5)44441210700 (6)4555 8900 (7)42441410400
Sulfonic-acid-generating compounds
Compound (1-1)
32 g of t-butyl acetoacetate was dissolved in tetrahydrofuran, the solution was cooled to 0 ° C. under a nitrogen atmosphere, and then 1.2 equivalents of sodium chloride was added thereto, followed by further dropwise addition of 40 g of methyl iodide. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 3 hours. At the end of the reaction, distilled water was poured into the resulting reaction mussel and extracted with ethyl acetate. The ethyl acetate layer containing the reaction product to be obtained was concentrated.
17 g of the obtained compound was mixed with 13 g of 37% aqueous formaldehyde solution and 6 ml of dioxane, followed by stirring. 7 g of potassium carbonate was slowly added thereto while maintaining the reaction temperature at 10 to 20 ° C. When the addition of potassium carbonate was finished, the reaction mixture was stirred for 8 hours while maintaining the reaction temperature. After the reaction was completed, sodium bicarbonate was added dropwise to the reaction mixture, and the mixture containing the desired reaction product was extracted with ethyl acetate. This was purified by silica gel top chromatography to obtain 20 g of the target reaction product (methylol compound).
Finally, 8 g of 2-chloride naphthalenesulfonyl, 6 g of the methylol compound obtained above were dissolved in THF. Under nitrogen atmosphere, the solution was cooled to 0 ° C, and 5 g of pyridine was added dropwise thereto. After the addition reaction was complete, the reaction mixture was neutralized and extracted with ethyl acetate / water. The reaction product containing the resulting organic layer was purified by silica gel top chromatography to obtain 8 g of compound (1-1) as a target compound.
Compound (1-6)
Compound (1-6) was obtained in the same manner as described above except that pentafluorobenzenesulfonyl chloride was used instead of naphthalenesulfonyl chloride.
Compound (2-3)
With ethylene glycol in the usual manner, the cyclic ketal was chemically converted to ethyl acetoacetate. The ketal was reduced with lithium hydroxide to obtain a ketal of acetoethanol. This ketal and camphorsulfonyl chloride were dissolved in THF. Under hydrogen atmosphere, the solution was cooled to 0 ° C, and excess pyridine was added dropwise thereto. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 10 hours. At the end of the reaction, the reaction mixture was neutralized and extracted with ethyl acetate / water. The reaction product obtained in the final organic layer was purified by silica gel top chromatography to obtain compound (2-3) as a target compound.
Compound (3-2)
Phenylcyclohexene was oxidized with osmium oxide to synthesize cis-diol, which was dissolved in THF together with 2-phthalic naphthalenesulfonyl. Under hydrogen atmosphere, the solution was cooled to 0 ° C, and excess pyridine was added dropwise thereto. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 10 hours. At the end of the reaction, the reaction mixture was neutralized and extracted with ethyl acetate / water. The reaction product obtained in the final organic layer was purified by silica gel top chromatography to obtain compound (3-2) as a target compound.
Compound (4-1)
Dimedon and 1.2 equivalents of naphtharensulfonyl pyridine chloride were dissolved in acetonitrile. Under hydrogen atmosphere, the solution was cooled to 0 ° C, and 2 equivalents of pyridine was added dropwise thereto. After the addition was complete, the reaction mixture was allowed to warm to room temperature and stirred for 8 hours. At the end of the reaction, the reaction mixture was neutralized and extracted with ethyl acetate / water. The reaction product obtained in the final organic layer was purified by silica gel top chromatography to obtain compound (4-1) as a target compound.
Compound (4-3)
Compound (1-6) was obtained in the same manner as the synthesis of compound (4-1), except that Meldrum's acid was used instead of dimedone.
Compound (5-2)
Compound (5-2) is described in the Journal of Photopolymer Science & Technology, Vol. 11, No. 3 (19 98), pp. It synthesize | combined according to the method described in 505-6.
To 1.4 g of each resin in Table 7 synthesized in the synthetic examples given above, 0.18 g of photo-acid generator, 10 mg of 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), The surfactants in Table 7 (amount of 1% by weight based on the total solid components of the composition) and the sulfone-acid-generating compounds in Table 7 (amount of 2% by weight based on the total solids of the composition) were added. . Each mixture was dissolved in propylene glycol monoethyl ether having a solid concentration of 14% by weight. This solution was purified with a 0.1-μm micro filter to prepare a positive photoresist composition solution of Examples 45-54.
In Table 7, PAG-1 represents triphenylsulfonium triflate, PAG-2 represents (PAG 4-35) synthesized above, and resin R3 represents a resin having the following structure.
Resin R3
In addition, the surfactant used is in the following.
W-1: Megapack F176 (Fluorine; manufactured by Dainippon Ink & Chemicals, Inc.)
W-2: Megapack R08 (Fluorinated Silicon; Dainippon Inks & Chemicals, Inc.)
W-3: Polysilonic Acid Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
W-4: Polyoxyethylene Nonylphenyl Ether
Evaluation test
Each obtained positive photoresist composition was applied to a silicon flake of a spin applicator, dried at 120 ° C. for 90 seconds to form a positive photoresist composition of about 0.5 μm thickness and the resist film was exposed to ArF excimer laser light. Each resist film was then heated at 120 ° C. for 90 seconds and then developed in a 2.38% aqueous tetraammonium hydroxide solution. Rinsing with distilled water yielded a resist pattern profile.
The number of phenomenon defects
Each 0.5 μm thick resist film attached to a 6-inch silicon substrate was dried at 20 ° C. for 60 seconds with a vacuum suction hot plate. This dried resist film was exposed with a Nikon stepper NSR-1505EX through a test mask with a contact hole pattern of 0.35 mu m, and heated at 120 DEG C for 90 seconds. The exposed resist film was then puddle-developed with a 2.38% aqueous TMAH solution for 60 seconds, rinsed with purified water for 30 seconds, and dried with a spin dryer. Each obtained sample was tested by LA-2112 which is a product of KLAK Tencol K.K., and the number of image development defects was grasped | ascertained. The main data obtained were considered as the number of developing defects.
Scum Development
A resist pattern with a line width of 0.22 mu m was evaluated as a developing residue. If no residue was observed, it was labeled "A", and if a significant amount of residue was observed, it was labeled "B".
Rebuild Line Width
The reproducibility of the line width (the amount of change in the line width) is expressed by the amount of change from the target line, which was determined by the following method. The resist pattern profile was formed five times by the above method when the target line width was 0.20 mu m. Each line width of this profile was measured with a scanning electron microscope. The change in line width of each profile was calculated from the background line width values, and the change amounts of the five total line widths obtained can be regarded as the line width reproducibility.
Line width change
│ (desk line width value)-(target line width value) │ × 100 / (target line width)
The results of this evaluation are shown in Table 7.
Acid-degradable resinsPhoto-acid generatorSulfonic acid-generating compoundsSurfactantsNumber of defectsScumLine width variation Example 45(One)One(1-1)-40A40 Example 46(2)2(2-3)-40A35 Example 47(3)One(3-2)-40A40 Example 48(4)2(4-1)-15A20 Example 49(2)2(2-3)W-440A25 Example 50(5)One(5-2)W-140A15 Example 51(6)One(1-6)W-230A15 Example 52(7)One(4-3)W-310A5 Example 53(4)One(4-1)W-110A5 Example 54(One)One(1-1)W-330A15 Comparative Example 3R3One(3-2)-15000B120
As apparent from the results given in Table 7, the resist composition of the comparative example had insufficient development defect number and scum generation. In contrast, the positive photoresist composition of the present invention was at a satisfactory level in development development prevention and scum prevention. Therefore, the resist composition of the present invention is suitable for lithography using far ultraviolet rays such as ArF excimer laser light. In addition, the resist composition of the present invention containing a special surfactant was not only free from developing defects but also excellent in regeneration of line width.
The present invention particularly provides a positive photoresist composition suitable for exposure light having a wavelength in the range of 170 nm to 220 nm, is effective in suppressing development defects and scums, imparts a desirable resist pattern profile, and provides excellent lines. It has width regeneration.
Although the invention has been described in detail with reference to specific embodiments, it is obvious that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.

权利要求:
Claims (7)
[1" claim-type="Currently amended] Compound (1) which generates an acid upon irradiation with actinic radiation or radiation,
Positive photoresist composition consisting of resin (2) containing a repeating unit having a group represented by formula (I):
-SO ₂ -OR- (Ⅰ)
(R represents an optionally substituted alkyl, cycloalkyl or alkenyl group, and the action of acid increases the dissolution rate in alkaline developing solution).
[2" claim-type="Currently amended] A linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having at least one hetero atom, and containing 3 to 30 carbon atoms, at least one substituent A positive photoresist composition having an alkenyl group having 2 to 6 carbon atoms.
[3" claim-type="Currently amended] The positive photoresist composition of claim 1, wherein the repeating unit is represented by the following formula (II):

(R ₁ to R ₃ each independently represent a group represented by a hydrogen atom, an alkyl group, a halogen atom, a cyano group, -SO ₂ -OR-, R represents an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, a divalent group consisting of two or more thereof).
[4" claim-type="Currently amended] Compound (1) which generates an acid upon irradiation with actinic radiation or radiation, and an alkali-soluble group protected by a partial structure containing an alicyclic hydrocarbon and represented by at least one of formulas (pI) to (pVI) below And a photoresist composition for exposure to ultraviolet rays, comprising a resin (2) decomposed by the action of an acid to increase solubility in alkali, and a compound (3) decomposed by the action of an acid to generate sulfonic acid:

(R ₁₁ represents a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl group; Z represents a group of atoms necessary to form an alicyclic hydrocarbon group together with a carbon atom;
R ₁₂ to R ₁₆ represent linear and branched alkyl groups each containing 1 to 4 carbon atoms, if at least one of R ₁₂ to R ₁₄ or one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group do;
If at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group and one of R ₁₉ and R ₂₁ is a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, then R ₁₇ to R ₂₁ Each independently represents a hydrogen atom, a linear and branched alkyl group containing 1 to 4 carbon atoms, and an alicyclic hydrocarbon group;
If at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group, R ₂₂ to R ₂₅ each independently represent a linear and branched alkyl or alicyclic hydrocarbon group containing 1 to 4 carbon atoms).
[5" claim-type="Currently amended] The positive photoresist composition for ultraviolet exposure according to claim 4, which contains fluorine and / or silicone surfactant.
[6" claim-type="Currently amended] 5. A repeating unit protected by a partial structure containing an alicyclic hydrocarbon group, wherein the repeating unit having an alkali soluble group represented by at least one of formulas (pI) to (pVI) is represented by the following formula (pA). Positive photoresist compositions for far ultraviolet exposure:

(R is the same or different and each represents a linear and branched alkyl group containing a hydrogen atom, a halogen atom or optionally substituted 1-4 carbon atoms; A represents a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and HA minute selected from a group consisting of a component or display a composite consisting of two or more components; R _a is represented by the general formula (pⅠ) ~ group represented by any of (pVI)).
[7" claim-type="Currently amended] The positive photoresist composition for ultraviolet exposure according to claim 4, wherein the compound which is decomposed by the action of an acid to generate sulfonic acid is represented by any one of formulas (1) to (5):

(R 'represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group);
R ' ₀ represents a group, such as -COOR ₀ , which is a group which decomposes under the action of an acid;
R ' ₁ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group;
R ' ₂ represents an alkyl group or an aralkyl group;
R ' ₃ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group;
R ' ₄ and R' ₅ represent an alkyl group if they combine with each other to form a ring;
R ' ₆ represents a hydrogen atom or an alkyl group;
R ' ₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group;
R ' ₈ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group;
R ' ₉ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group if R' ₉ is bonded to R ' ₇ to form a ring;
R _'10 represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group;
R _'11 is R' ₁₀ and, if R _'11 form a ring by combining to each other, represents an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group, an alkenyl group).

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US6576392B1|2003-06-10|

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KR100610165B1|2006-08-09|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1998-12-07|Priority to JP34719398

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1998-12-07|Priority to JP98-347193

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1999-02-08|Priority to JP99-30209

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1999-02-08|Priority to JP03020999A

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1999-08-26|Priority to JP99-240600

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1999-08-26|Priority to JP24060099A

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1999-12-06|Application filed by 무네유키 가코우, 후지 샤신 필름 가부시기가이샤

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2000-07-25|Publication of KR20000047927A

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2006-08-09|Application granted

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2006-08-09|Publication of KR100610165B1

优先权:

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申请号 | 申请日 | 专利标题

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JP34719398|1998-12-07|

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JP98-347193|1998-12-07|

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JP99-30209|1999-02-08|

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JP03020999A|JP3912761B2|1999-02-08|1999-02-08|Positive photoresist composition for deep ultraviolet exposure|

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JP99-240600|1999-08-26|

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JP24060099A|JP3995369B2|1998-12-07|1999-08-26|Positive photoresist composition|