JP2003307840A - Positive photoresist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photoresist composition excellent in line edge roughness and PED stability and a positive photoresist composition excellent also in sensitivity. <P>SOLUTION: A positive photoresist composition is provided which comprises (a) a resin which is decomposed by the action of an acid to increase solubility in an alkali developing solution and (b) a compound which has a specified oxime sulfonate structure and generates an acid upon irradiation with an actinic ray or a radiation and a compound which has a specified onium salt structure and generates an acid upon irradiation with an actinic ray or a radiation. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used for manufacturing semiconductor integrated circuit devices, integrated circuit manufacturing masks, printed wiring boards, liquid crystal panels and the like.

[0002]

2. Description of the Related Art As a positive photoresist composition, a chemically amplified resist described in Patent Document 1 (US Pat. No. 4,491,628), Patent Document 2 (European Patent No. 29,139), etc. There is a composition. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction causes the solubility in the developing solution of the irradiated area and the non-irradiated area of active radiation. Is a pattern forming material that changes the temperature and forms a pattern on the substrate.

The above chemically amplified positive resist composition comprises an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (photo-acid generator), and a dissolution inhibiting compound for an alkali-soluble resin having an acid-decomposable group. A three-component system, a two-component system comprising a resin having a group which is decomposed by reaction with an acid to be alkali-soluble and a photoacid generator, and a resin having a group which is decomposed by reaction with an acid to be alkali-soluble, It can be roughly classified into a hybrid system composed of a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photo-acid generator.

Performance is obtained by mixing two or more resins (acid-decomposable resins) which are decomposed by the action of an acid used in the above chemically amplified positive resist composition to increase the solubility in an alkali developing solution. Various techniques for improvement are known. Further, Patent Document 3 (European Patent Application Publication No. 10
No. 24406) describes a technique of improving performance by mixing two or more acid-decomposable resins with a photo-acid generator. In addition, Patent Document 4 (Japanese Patent Laid-Open No. 2001-166478)
No.) proposed the use of a resin containing a repeating unit having an acid-eliminating alicyclic alkyl group in the side chain and a polyhydroxystyrene repeating unit in order to solve the problems of PED stability and standing wave. There is.

However, it has been desired to suppress the dimensional variation by improving the line edge roughness and the PED stability accompanying the pattern miniaturization. Here, the edge roughness means that the edge of the resist pattern and the substrate interface fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that looks uneven. The unevenness is transferred by the etching process using the resist as a mask and deteriorates the electrical characteristics, thus lowering the yield. Especially 0.25
In the ultrafine region of μm or less, the edge roughness is an extremely important issue for improvement. In addition, PED (Post Exposur
e Delay) stability refers to the stability of a coating film when it is left in an exposure device or a coating device until a heating operation is performed after exposure.

[0006]

[Patent Document 1] US Pat. No. 4,491,628

[Patent Document 2] European Patent No. 29139

[Patent Document 3] European Patent Application Publication No. 1024406

[Patent Document 4] Japanese Patent Laid-Open No. 2001-166478

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a chemically amplified positive photoresist composition having excellent line edge roughness and PED stability, and further a chemically amplified positive photoresist composition having excellent sensitivity. It is to provide a resist composition.

[0008]

The present inventors have made diligent studies in view of the present situation, and as a result, by using a positive photoresist composition containing an acid-decomposable resin and two or more photoacid generators. The above objects have been achieved and the present invention has been completed. That is, the positive photoresist composition according to the present invention has the following constitution.

(1) (a) a resin which is decomposed by the action of an acid to increase its solubility in an alkaline developer, and (b) an acid is generated by irradiation with an actinic ray or radiation represented by the following general formula (1). And a compound having at least one selected from the group of compounds that generate an acid upon irradiation with actinic rays or radiation represented by the following general formulas (2) to (4). Resist composition.

[0010]

[Chemical 5]

In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a cyano group. R ₁ and R ₂ may combine to form a ring. R ₃ represents an alkyl group or an aryl group. Further, R ₁ and R ₂ are a single bond or a linking group, and are R ₁ or R ₂ of another compound represented by the general formula (1).
May be combined with.

[0012]

[Chemical 6]

In the general formulas (2) to (4), R _{11 to} R ₁₉ are
Each independently represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group. X ⁻ represents a hydroxide anion or a carboxylic acid anion having a molecular weight of 100 or less.

(2) The resin (a) is represented by a repeating unit having a group represented by the general formula (X), and a repeating unit having a group represented by the general formula (Y1) and a general formula (Y2). The positive photoresist composition as described in (1) above, which is a resin having at least one of a repeating unit having a group represented by:

[0015]

[Chemical 7]

In the general formula (X), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group. Z represents an alkyl group. m represents an integer of 1 to 20.

[0017]

[Chemical 8]

In the general formula (Y1), R ₂₀ represents an alkyl group. In the general formula (Y2), R ₂₁ and R ₂₂ are
Each independently represents an alkyl group.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

(A) A resin which decomposes due to the action of an acid to increase its solubility in an alkaline developer (resin (a))

The resin having a group capable of decomposing by the action of an acid (also referred to as an acid decomposable group) in the present invention has a structure in which an acid decomposable group is introduced into a compound having a molecular weight distribution obtained by polymerizing a monomer. And a compound which becomes alkali-soluble by the action of an acid.

The resin having an acid-decomposable group is a resin having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and the side chain. Of these, a resin having an acid-decomposable group in its side chain is more preferable.

Next, as the base resin when the acid-decomposable group is bonded as a side chain, --OH or --COO is attached to the side chain.
H, preferably -R ⁰ -COOH or -Ar-OH
It is an alkali-soluble resin having a group. Where -R ⁰
-Represents a divalent or higher valent aliphatic or aromatic hydrocarbon which may have a substituent, and -Ar- represents a divalent or higher valent aromatic group which may have a monocyclic or polycyclic substituent. Represent

The base resin preferred in the present invention is an alkali-soluble resin having a phenolic hydroxyl group. The alkali-soluble resin having a phenolic hydroxyl group used in the present invention is o-, m- or p-hydroxystyrene (collectively referred to as hydroxystyrene), or o-, m- or p-hydroxy-α-. A copolymer or homopolymer thereof containing at least 30 mol%, preferably 50 mol% or more of a repeating unit corresponding to methylstyrene (collectively referred to as hydroxy-α-methylstyrene), or a benzene nucleus of the unit. Is preferably a partially hydrogenated resin, more preferably a p-hydroxystyrene homopolymer. As monomers other than hydroxystyrene and hydroxy-α-methylstyrene for preparing the copolymer by copolymerization, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, Maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes and alkylstyrenes are preferable, and styrene, acetoxystyrene and t-butylstyrene are more preferable.

In the present invention, as the resin (a), if it is a resin whose solubility in an alkaline developer is increased,
Any of these may be used, but examples thereof include those shown below.

[0026]

[Chemical 9]

In the above formula, W represents an acid-decomposable group. R ¹⁴ represents an acid stable group.

As the acid-decomposable group of W, a group represented by the following general formula (X), a group represented by the following general formula (X1), a group represented by the following general formula (X2), and the following general formula Expression (X
Examples of the group represented by 3) include the following general formula (X)
The group represented by is preferable.

[0029]

[Chemical 10]

[0030]

[Chemical 11]

In the general formula (X), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group. Z represents an alkyl group. m represents an integer of 1 to 20.

R in the general formulas (X1) to (X3),
R ′ and R ″ may be the same or different and each is an alkyl group, which may have a substituent. Further, R ′ and R ″ may be bonded to each other to form a ring (for example, a 3 to 12-membered ring).

As the alkyl group as R ₄ and R ₅ ,
It may be linear, branched, or cyclic, and may have a substituent. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and an n-decanyl group. To be The branched alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and includes, for example, i-propyl group, i-butyl group, t-butyl group,
i-pentyl group, t-pentyl group, i-hexyl group, t
-Hexyl group, i-heptyl group, t-heptyl group, i-
Examples thereof include an octyl group, a t-octyl group, an i-nonyl group and a t-decanoyl group. The cyclic alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and tetra. Examples thereof include cyclododecanyl group.

The alkyl group as Z in formula (X) may be linear, branched or cyclic, and may have a substituent.

The linear or branched alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. , T-butyl group, n-pentyl group, i
-Pentyl group, t-pentyl group, n-hexyl group, i-
Hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t-heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t- Nonyl group, n-decanyl group, i-decanyl group,
Examples thereof include t-decanyl group. The cyclic alkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

R in the general formulas (X1) to (X3),
The alkyl group as R ′ and R ″ preferably has 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, t-butyl group, n-pentyl group, i-pentyl group,
t-pentyl group, n-hexyl group, i-hexyl group, t
-Hexyl group, n-heptyl group, i-heptyl group, t-
Heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, i-decanyl group, t-decanyl group and the like. be able to.

Further, as the substituent of each of the above groups, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, the above cycloalkyl group, a methoxy group, an ethoxy group. , Hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-
Alkoxy group such as butoxy group, methoxycarbonyl group,
Alkoxycarbonyl group such as ethoxycarbonyl group, benzyl group, phenethyl group, aralkyl group such as cumyl group,
Aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanamyl groups, valeryl groups, and other acyl groups, butyryloxy groups, and other acyloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups. And an aryloxy group such as a phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group. These substituents may further have a substituent.

The group which is not decomposed by the action of an acid in R ¹⁴ (referred to as an acid stable group) includes a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and an acyloxy group.
In the acid stable group of R ¹⁴ , the alkyl group is preferably a group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group.

As the alkoxy group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an n-butoxy group, an isobutoxy group,
An alkoxy group having 1 to 4 carbon atoms such as a sec-butoxy group is preferable. As the acyloxy group, those having 2 to 7 carbon atoms such as acetoxy group, propnoyloxy group, butanoyloxy group and benzoyloxy group are preferable.

Specific examples of the group represented by formula (X) are shown below, but the group is not limited to these.

[0041]

[Chemical 12]

The resin (a) may be any resin as long as the alkali developability is increased by the action of an acid, but it has a group represented by the above general formula (X) and is decomposed by the action of an acid. Preferable is a resin (also referred to as a resin having a group represented by the following general formula (X)) whose solubility in an alkaline developer is increased.

In the present invention, the content of the repeating unit (structural unit) having a group represented by the general formula (X) in such a resin is from 5 mol% to 50 mol% based on all repeating units. Preferably, more preferably 5 mol%
It is 30 mol%.

In the present invention, the resin having a group represented by the general formula (X) may contain other acid-decomposable group in addition to the group represented by the general formula (X).

The resin containing the group represented by the general formula (X) is prepared by synthesizing the corresponding vinyl ether and reacting it with a phenolic hydroxyl group-containing alkali-soluble resin dissolved in a suitable solvent such as tetrahydrofuran by a known method. Can be obtained at The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, hydrochloric acid, p-toluenesulfonic acid, or a salt such as pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active raw material such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction,
It can also be synthesized using mercury or a palladium catalyst. As another method, it can be synthesized by a method of acetal exchange using a corresponding alcohol and vinyl ether. In this case, it is carried out in the presence of an acid such as p-toluenesulfonic acid or pyridinium tosylate by allowing the alcohol to have a substituent to be introduced and mixing a relatively unstable vinyl ether such as t-butyl vinyl ether as the vinyl ether. .

In the resin (a), the repeating unit having a group represented by the general formula (X) is represented by the following general formula (V
The structural unit represented by I) may be mentioned.

[0047]

[Chemical 13]

The substituent W ₁ in the general formula (VI) represents a group represented by the general formula (X).

Specific structures of the structural unit represented by the general formula (VI) are shown below, but the invention is not limited thereto.

[0050]

[Chemical 14]

[0051]

[Chemical 15]

Preferred repeating units copolymerizable with the general formula (VI) include the following general formula (VII) and the following general formula (V
The structural unit represented by III) can be mentioned. By incorporating the above-mentioned structural unit into the resin, the resin is decomposed by the action of an acid, and the solubility in an alkali developing solution can be controlled. Also, by introducing this structural unit, a profile with excellent rectangularity can be achieved.
Furthermore, it is effective for adjusting the amount of the structural unit represented by the general formula (VI).

[0053]

[Chemical 16]

The group which is not decomposed by the action of an acid in R ¹⁴ (referred to as an acid stabilizing group) includes a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and an acyloxy group.
In the acid stable group of R ¹⁴ , the alkyl group is preferably a group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group.

As the alkoxy group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group,
An alkoxy group having 1 to 4 carbon atoms such as a sec-butoxy group is preferable. As the acyloxy group, those having 2 to 7 carbon atoms such as acetoxy group, propnoyloxy group, butanoyloxy group and benzoyloxy group are preferable.

Specific examples of the polymerizable monomer having the structural unit represented by the general formula (VIII) include, but are not limited to, the followings.

[0057]

[Chemical 17]

[0058]

[Chemical 18]

The resin containing the structural unit represented by the general formula (VII) or (VIII) can be obtained by reacting a phenol resin or a monomer thereof with an acid anhydride in the presence of a base, or a corresponding halide in the presence of a base. Can be obtained by reacting with.

As the resin (a), the above-mentioned general formula (VI),
General formula (VII), general formula (VI), general formula (VII), general formula (VIII), general formula (VI), general formula (VII) and t-butyl acrylate Can be mentioned.

The resin (a) is preferably a blend containing a resin (resin (A ')) having the following general formula (VI), general formula (VII) or general formula (VIII) shown below. .

[0062]

[Chemical 19]

In the general formulas (VI) to (VIII), R ¹⁴ represents the acid stable group. W ₁ represents a group represented by the general formula (X). x and y are 1 to 100, z is 0 to 100, but x +
y + z = 100

In the resin (a) composed of the general formula (VI) or the general formula (VII), the content ratio of the repeating unit represented by the general formula (VI) is 10 mol% or more and 45 mol% or less,
It is preferably 15 mol% or more and 40 mol% or less.

The above general formula (VI), general formula (VII) and t-
The content ratio of each repeating unit in the resin composed of butyl acrylate is such that the general formula (VI) is 0 mol% to 20 mol% and the t-butyl acrylate is 5 mol% to 25 mol%, preferably the general formula (VI ) Is 5 mol% or more 2
The amount of t-butyl acrylate is 0 mol% or less and 10 mol% or more and 20 mol% or less.

The x, y and z ratios of the resin (A ') which the resin (a) may contain preferably satisfy the following conditions.

When z = 0, 0.05 <x / (x + y) <0.50, more preferably 0.1 <x
When /(x+y)<0.45z>0 0.05 <x / (x + y + z) <0.35, 0.005 <z / (x + y + z) <0.25, x ≧ z, 0.5 <x / (x + z) <0.95 More preferably 0.1 <x /(X+y+z)<0.25, 0.01 <z / (x + y + z) <0.15, x ≧ z, 0.5 <x / (x + y) <0.85

When the resin of the present invention satisfies the above conditions, the rectangularity of the profile is improved, and especially the development defect is further improved.

The repeating structural unit represented by the general formula (VI), the general formula (VII) or the general formula (VIII), or the repeating structural unit derived from another polymerizable monomer may be a single type or a combination of two or more types. It may be present in the resin. The resin (a) contained in the positive photoresist composition of the present invention may have an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group introduced therein in order to maintain good developability in an alkali developing solution. Other polymerizable monomers suitable for the above may be copolymerized.

The specific structure of the resin (a) of the present invention is illustrated below, but the present invention is not limited thereto.

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

[0074]

[Chemical formula 23]

[0075]

[Chemical formula 24]

[0076]

[Chemical 25]

The resin (a) includes a repeating unit having a group represented by the general formula (X) and a general formula (Y
A repeating unit having a group represented by 1) and a general formula (Y
A resin having at least one of the repeating units having a group represented by 2) is preferable in terms of improving PED stability and sensitivity.

[0078]

[Chemical formula 26]

In the general formula (Y1), R ₂₀ represents an alkyl group. In the general formula (Y2), R ₂₁ and R ₂₂ are
Each independently represents an alkyl group. The alkyl group for R _{20 to} R ₂₂ may be linear or branched and has 1 to 1 carbon atoms.
8 is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. R ₂₀ , R
The alkyl group as ₂₁ and R ₂₂ may have a substituent, and examples of the substituent include an alkoxy group (preferably having a carbon number of 1 to 4, for example, a methoxy group, an ethoxy group, a hydroxyethoxy group, Linear or branched propoxy group, linear or branched butoxy group), halogen atom (for example, fluorine atom, chlorine atom, iodine atom), cyano group, hydroxy group, carboxy group, nitro group, aryl group (preferably having 6 carbon atoms). To 14, for example, phenyl group, naphthyl group, aryloxy group (preferably having 6 to 1 carbon atoms)
4) and alkylthio groups (preferably having 1 to 4 carbon atoms).

As the repeating unit having a group represented by the general formula (Y1) and the repeating unit having a group represented by the general formula (Y2), a repeating unit represented by the following general formula (Y) is preferable.

[0081]

[Chemical 27]

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is 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, or a urea group, alone or in combination of two or more. Represents a combination of groups. The group as A preferably has 20 or less carbon atoms, and more preferably a single bond. Y is the general formula (Y1) or (Y
It represents a group represented by 2).

Specific examples of the repeating unit having a group represented by the general formula (Y1) and the repeating unit having a group represented by the general formula (Y2) are shown below, but the present invention is not limited thereto.

[0084]

[Chemical 28]

Below, at least one of a repeating unit having a group represented by the general formula (X), a repeating unit represented by the general formula (Y1) and a repeating unit represented by the general formula (Y2). Specific examples of the resin having a are given below, but the invention is not limited thereto.

[0086]

[Chemical 29]

[0087]

[Chemical 30]

[0088]

[Chemical 31]

As the resin (a), a repeating unit having a group represented by the general formula (X), which is a preferable resin, and a repeating unit represented by the general formula (Y1) and a general formula (Y2) are represented. In the resin having at least one of the repeating units described above, the content of the repeating unit having a group represented by the general formula (X) is 5 mol% to 50 with respect to all repeating units constituting the resin. Mol% is preferable, and more preferably 5 mol% to 30 mol%. The content of the repeating unit having a group represented by the general formula (Y1) and the repeating unit having a group represented by the general formula (Y2) is 5 mol as a total amount with respect to all repeating units constituting the resin. % To 30 mol%, more preferably 5 to 20 mol%.

The molecular weight of the resin (a) is the weight average (Mw:
The polystyrene standard) is usually 2,000 or more, preferably 3,000 to 200,000, and more preferably 5,000 to 70,000. Also, the degree of dispersion (Mw
/ Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, and particularly preferably 1.0 to 3.0. The smaller the degree of dispersion, the higher the heat resistance and the image formation. The properties (pattern profile, defocus latitude, etc.) are improved.

The content of the resin (a) in the positive photoresist composition (excluding the coating solvent) is preferably 50-9.
It is 9% by weight, more preferably 75 to 98% by weight.

(B) Compounds which generate an acid upon irradiation with actinic rays or radiation represented by the general formula (1), and by irradiation with actinic rays or radiations represented by the general formulas (2) to (4). Compound that generates an acid The resist composition of the present invention is
A compound represented by the above general formula (1) as a compound (photoacid generator) that generates an acid by an actinic ray or radiation that is irradiated during patterning, such as KrF excimer laser light, ArF excimer laser light, or electron beam. And at least one selected from the compounds (onium compounds) represented by the general formulas (2) to (4).

In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a cyano group. R ₁ and R ₂ may combine to form a ring. R ₃ represents an alkyl group or an aryl group. Further, R ₁ and R ₂ are a single bond or a connecting chain, and R ₁ or R ₂ of another compound represented by the general formula (1) is present.
May be combined with.

Each of R ₁ and R ₂ preferably has _{1 to} 16 carbon atoms and may have a substituent. R ₃
Each group as is preferably has 1 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, and may have a substituent. R
The alkyl group as ₁ , R ₂ and R ₃ may be linear, branched or cyclic, and is preferably an alkyl group having 1 to 16 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a t-amyl group, an n-hexyl group, and an n-hexyl group. Octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, alkyl group such as hexadecyl group, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t-butyl group, perfluorooctyl group, Examples thereof include a perfluoroundecyl group and a 1,1-bistrifluoromethylethyl group. The cyclic alkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group as R ₁ and R ₂ may be linear, branched or cyclic, and has 2 to 2 carbon atoms.
16 alkenyl groups are preferred. Examples of the linear or branched alkenyl group include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5
-Hexenyl group, 2-oxo-3-pentenyl group, decapentaenyl group, 7-octenyl group and the like. As the cyclic alkenyl group, a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.
2.4] Dodeca-3,7-dien-5-yl group and the like can be mentioned.

The alkynyl group as R ₁ and R ₂ preferably has 2 to 16 carbon atoms and includes, for example, an ethynyl group, a propargyl group, a 2-butynyl group, a 4-hexynyl group, a 2-octynyl group, a phenylethynyl group and a cyclohexyl group. Examples thereof include an ethynyl group.

The aryl group as R ₁ , R ₂ and R ₃ is
More preferably, it has 5 to 16 carbon atoms, and still more preferably, those having 6 to 14 carbon atoms such as phenyl group, tolyl group, methoxyphenyl group, and naphthyl group. The heterocyclic group preferably has 5 to 16 carbon atoms, and examples thereof include those in which the ring-constituting atom of the aryl group is replaced with a heteroatom, for example, a thiophenfuryl group,
Examples thereof include a thienyl group.

As the substituent which each of the above groups may have
Is, for example, an alkyl group (eg, R ₁Archi as
The same as those of the radicals, preferably having 1 to 4 carbon atoms,
Xy group (preferably having 1 to 4 carbon atoms, for example, methoxy
Group, ethoxy group, hydroxyethoxy group, straight or branched
Propoxy group, linear or branched butoxy group), halogen source
Child (eg, fluorine atom, chlorine atom, iodine atom), shear
Group, hydroxy group, carboxy group, nitro group, aryl
Roxy group (preferably having 6 to 14 carbon atoms), alkyl group
O group, aralkyl group (preferably having 6 to 14 carbon atoms, for example
Benzyl group, naphthylmethyl group), the following general formula (1
Examples include groups represented by A).

[0099]

[Chemical 32]

In the above formula, R _{1 and} R ₂ are each represented by the general formula (1).
It has the same meaning as R _{1 to} R ₂ in the above.

Specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0102]

[Chemical 33]

[0103]

[Chemical 34]

In the above general formulas (2) to (4), R _{11 to} R ₁₉
The alkyl group of has preferably 1 to 10 carbon atoms, and is methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, t-amyl group, n.
-Hexyl group, n-octyl group, i-octyl group and the like. The cycloalkyl group of R _{11 to} R ₁₉ preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.

The acyl group for R _{11 to} R ₁₉ is preferably an acetyl group, a propanoyl group, a butanoyl group, 2,
Examples thereof include a 2-dimethylpropanoyl group, a cyclohexylcarbonyl group and a benzoyl group.

The aryl group of R _{11 to} R ₁₉ preferably has 4 to 12 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a methoxyphenyl group and a naphthyl group.

Each of the above groups may have a substituent,
As the substituent, an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom (fluorine atom, chlorine atom, iodine atom), a cyano group, a hydroxy group, a carboxy group, a nitro group, an aryloxy group, an alkylthio group, an aralkyl group, etc. Is mentioned. Here, the alkyl group and the cycloalkyl group have the same meanings as described above. As the alkoxy group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group,
1 carbon atom such as sec-butoxy group and t-butoxy group
Up to four. Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group and a thienyl group.

In the above general formulas (2) to (4), X ⁻ represents a hydroxide anion or a carboxylic acid anion having a molecular weight of 100 or less. Examples of carboxylic acid anions having a molecular weight of 100 or less include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, lactic acid, hydroxyacetic acid and oxalic acid.

Specific examples of the compounds represented by the general formulas (2) to (4) are shown below, but the invention is not limited thereto.

[0110]

[Chemical 35]

[0111]

[Chemical 36]

The compound represented by the general formula (1) is, for example,
SRSandler & W.Karo, Organic functional group prepa
rations, Vol. 3, Academic Press), for example, by reacting a ketone with hydroxylamine or a salt thereof, or by nitrosating an “active” methylene group with nitrous acid or alkyl bisulfite. It can be obtained by reacting an oxime compound with a desired acid halide.

Compounds which generate an acid upon irradiation with actinic rays or radiation represented by the general formula (1) and acid upon irradiation with actinic rays or radiation represented by the general formulas (2) to (4) It contains at least one selected from the group of compounds that occur.

Compounds which generate an acid upon irradiation with actinic rays or radiation represented by the above general formula (1) and acid upon irradiation with actinic rays or radiation represented by the above general formulas (2) to (4) The used amount of at least one selected from the group of compounds that generate is a molar ratio (a compound that generates an acid upon irradiation with actinic rays or radiation represented by the above general formula (1) /
At least one compound selected from the group of compounds which generate an acid upon irradiation with actinic rays or radiation represented by the above general formulas (2) to (4)), and usually 95/5 to 20/80, preferably 95. / 5 to 40/60, more preferably 80/2
It is 0 to 50/50.

The addition amount of the compound which generates an acid upon irradiation with actinic rays or radiation represented by the above general formula (1) is usually 0.1 to 7% by weight, based on the solid content in the composition.
Preferably 0.2 to 5% by weight, more preferably 0.2 to
It is 4% by weight.

The amount of at least one compound selected from the group of compounds which generate an acid upon irradiation with actinic rays or radiations represented by the above general formulas (2) to (4) is such that the solid content in the composition is As a standard, it is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight, and more preferably 0.1 to 2% by weight.

In the present invention, other photoacid generator may be used in combination with the compounds represented by the above general formulas (1) to (4).

The addition amount (total amount) of the photo-acid generator is usually in the range of 0.11 to 40% by weight, preferably 0.2 to 20% by weight, and more preferably 0.2 to 20% by weight, based on the solid content in the composition. It is preferably used in the range of 1 to 10% by weight. If the addition amount of the photo-acid generator is less than 0.11% by weight, the sensitivity tends to be low, and if the addition amount is more than 40% by weight, the light absorption of the resist becomes too high and the profile is deteriorated. Process (especially bake) margin tends to be narrowed.

An organic basic compound can be used in the composition of the present invention. This is preferable because stability during storage is further improved and line width change due to PED is further reduced. The preferred organic basic compound that can be used in the present invention is a compound that is more basic than phenol. Of these, nitrogen-containing basic compounds are preferable. As a preferable chemical environment, the following formulas (A) to (E) can be mentioned.

[0120]

[Chemical 37]

More preferred compounds are nitrogen-containing cyclic compounds (also called cyclic amine compounds) or nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule. The cyclic amine compound more preferably has a polycyclic structure. Specific preferred examples of the cyclic amine compound include compounds represented by the following general formula (F).

[0122]

[Chemical 38]

In formula (F), Y and Z each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom and may be substituted. Here, examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom. The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Furthermore, specific examples of the compound represented by the general formula (F) include the compounds shown below.

[0124]

[Chemical Formula 39]

Among the above, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferable.

The nitrogen-containing basic compound having two or more nitrogen atoms having different chemical environments in one molecule is particularly preferably a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Alternatively, it is a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples thereof include morpholine and substituted or unsubstituted aminoalkylmorpholine. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine , 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6.
-Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,6
-Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine ,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, trimethylimidazole,
Examples thereof include triphenylimidazole and methyldiphenylimidazole, but are not limited thereto.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the positive photoresist composition (excluding the solvent). 0.001
If the amount is less than 10 parts by weight, the above effect tends not to be obtained, and 10
If it exceeds the weight part, the sensitivity tends to decrease and the developability of the non-exposed area tends to deteriorate.

If necessary, the chemically amplified positive photoresist composition of the present invention further comprises a surfactant, a dye, a pigment, a plasticizer, a photosensitizer, and a phenolic OH which promotes solubility in a developing solution. A compound having two or more groups and the like can be contained.

The positive photoresist composition of the present invention preferably contains a surfactant. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Eftop EF301, E
F303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173, F176, F189, R0
8 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluoro FC
430, FC431 (Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC10.
1, SC102, SC103, SC104, SC10
5, fluorine-containing surfactants such as SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, no. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) and the like. Among these surfactants, fluorine-based or silicon-based surfactants are preferable from the viewpoint of coatability and reduction of development defects.

The content of the surfactant is usually 0.01% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the total solid content of the composition of the present invention. is there. These surfactants can be used alone or in combination of two or more.

Further, the following chemical sensitization type positive resist of the present invention is added by adding a spectral sensitizer as described below to sensitize the photo-acid generator to be used in a longer wavelength region than far ultraviolet which has no absorption. Can be made sensitive to the i or g line. Specific examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene and pyrene. , Perylene,
Phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline. , N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-
Benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,2
-Naphthoquinone, 3,3'-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but not limited to these.

Examples of the compound having two or more phenolic OH groups for promoting the solubility in the developing solution include polyhydroxy compounds, and the polyhydroxy compounds are preferably phenols, resorcin, phloroglucin, phlorogluside, and 2, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, tris ( There are 4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and 1,1′-bis (4-hydroxyphenyl) cyclohexane.

The chemically amplified positive photoresist composition of the present invention is prepared by dissolving each of the above-mentioned components in a solvent that dissolves it and coating it on a support. Solvents that can be used include ethylene dichloride and cyclohexanone. , Cyclopentanone, 2-heptanone, γ-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, pyruvin Ethyl acid, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or as a mixture.

The chemically amplified positive photoresist composition is a spinner on a substrate (eg, silicon / silicon dioxide coating) such as used in the manufacture of precision integrated circuit devices.
A good resist pattern can be obtained by applying an appropriate coating method such as a coater, exposing through a predetermined mask, baking and developing.

Examples of the alkaline developer of the chemically amplified positive photoresist composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, aqueous ammonia and the like. Inorganic alkalis, primary amines such as ethylamine and n-propylamine, diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl ( 2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanol Ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabu Quaternary ammonium salts such as Le ammonium hydroxide, pyrrole, alkali aqueous solution, such as cyclic amines such as piperidine (typically 0.1 to 10
% By weight, etc.

[0137]

EXAMPLES The present invention will be described in more detail below, but the present invention is not limited thereto.

Synthesis Example 1 [Synthesis Example of Resin] The resin can be synthesized by any method of acetalization using a vinyl ether or an acetal exchange method using an alcohol and an alkyl vinyl ether. Further, the dehydration azeotropic method as shown below can be preferably used for efficient and stable synthesis. However, these synthesizing methods are examples, and the present invention is not limited to these.

(1) Synthesis of Resin 1 VP8000 (1800 g) manufactured by Nippon Soda and propylene glycol monomethyl ether acetate (PGMEA)
(8200 g) was dissolved in a flask and vacuum distillation was performed to distill off water and PGMEA azeotropically. After confirming that the water content was sufficiently low, cyclohexaneethanol (5
76.2 g) to which pyridinium-p-toluenesulfonate (9.0 g) was dissolved and added to the reaction solution, and t-butyl vinyl ether (450.2 g) was added.
g) was added, and the mixture was stirred at room temperature for 5 hours. Water (3.6 liters) and ethyl acetate (7.2 liters) were added to the reaction solution, the layers were separated, washed with water, and then distilled under reduced pressure to remove ethyl acetate, water, and azeotrope PGMEA. Alkali-soluble resin having a substituent according to the present invention (Resin 1)
(30 wt% PGMEA solution) was obtained. In addition, the Mw of the obtained polymer was measured by GPC measurement using polystyrene standards.
Was 11000 and Mw / Mn was 1.10.

(2) Synthesis of Resin 2 VP15000 (100 g) manufactured by Nippon Soda and PGMEA
(400 g) was dissolved in a flask and vacuum distillation was performed,
Water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, ethyl vinyl ether (25.0
g) and p-toluenesulfonic acid (0.02 g) were added,
The mixture was stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, and water (400 m
l) and ethyl acetate (800 ml) were added, the mixture was separated, washed with water, and then distilled under reduced pressure to distill off ethyl acetate, water and azeotrope PGMEA to give an alkali-soluble resin having a substituent according to the present invention. (Resin 2) (30 wt% PGME
A solution) was obtained. In addition, by the GPC measurement based on polystyrene, the Mw of the obtained polymer was 18,000, Mw /
Mn was 1.12.

(3) Synthesis of Resin 3 16.2 g of poly (p-hydroxystyrene) and isopropylate chloride were dissolved in 100 ml of acetone, 1.8 g of triethylamine was added to the reaction solution, and the mixture was stirred at 50 to 55 ° C. for 5 hours. did. The reaction solution was transferred to 1000 ml of water, and the upper layer was removed by decantation. The viscous resinous material obtained was dissolved in 75 ml of acetone and the solution was transferred into 500 ml of water. The precipitated rubbery resin was dried under reduced pressure to give poly (p-hydroxystyrene /
15.4 g of p-isopropoxystyrene) was obtained as a white powder. The ratio of p-hydroxystyrene structural unit to p-isopropoxystyrene structural unit of the obtained polymer was 90:10 by ¹ H-NMR. The weight average molecular weight Mw of the obtained polymer was 15500, and the molecular weight distribution Mw /
Mn was 1.12. 15.0 g of the above poly (p-hydroxystyrene / p-isopropoxystyrene) and 3.0 g of ethyl vinyl ether were added to 150 ml of ethyl acetate.
And p-toluenesulfonic acid in a catalytic amount was added thereto, followed by stirring at room temperature for 6 hours to allow the reaction to proceed. After the reaction, the synthetic product was neutralized with triethylamine and concentrated. The viscous oily residue was dissolved in 100 ml acetone and 3000 ml for further precipitation.
Moved into the water. The precipitated polymer was filtered, washed with water, and dried under reduced pressure to obtain 16.2 g of poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-isopropoxystyrene) as a white powder. The ratio of p-1-ethoxyethoxystyrene structural unit, p-hydroxystyrene structural unit and p-isopropoxystyrene structural unit in the obtained polymer was 30:60:10 by ¹ H-NMR. Also, the Mw of the obtained polymer was 1800 by GPC measurement based on polystyrene.
0, Mw / Mn was 1.12.

(4) Synthesis of Resin 4 [Synthesis Example 4-1 Synthesis of Vinyl Ether] Cyclohexylethyl alcohol was mixed with ethyl vinyl ether, and mercury acetate was added thereto to obtain 12 at room temperature.
Stir for hours. After extraction with ethyl acetate and water, washing with water, and distillation under reduced pressure, the target product, cyclohexylethyl vinyl ether (X-1), was obtained. [Synthesis Example 4-2] p obtained by dehydration and distillation purification based on a conventional method
-Tert-butoxystyrene monomer 39.6 g
(0.225 mol) and t-Bu styrene monomer 4 g
(0.025 mol) was dissolved in 100 ml of tetrahydrofuran. Polymerization reaction was carried out by adding 0.033 g of azobisisobutyronitrile (AIBN) three times at 2.5 hour intervals under a nitrogen stream and stirring at 80 ° C., and finally continuing stirring for further 5 hours. . The reaction solution is hexane 120
It was poured into 0 ml to precipitate a white resin. The obtained resin was dried and then dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added to this and hydrolyzed by heating under reflux for 6 hours and then reprecipitated in 5 L of ultrapure water. The resin was filtered off, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, added dropwise to 5 L of ultrapure water with vigorous stirring, and reprecipitated. This reprecipitation operation was repeated 3 times. The obtained resin is dried in a vacuum dryer at 120 ° C. for 12 hours.
After drying for an hour, a poly (p-hydroxystyrene / t-butylstyrene) copolymer alkali-soluble resin R-2 was obtained. The weight average molecular weight of the obtained resin was 9,600. [Synthesis Example 4-3] 20 g of the alkali-soluble resin R-2 obtained in Synthesis Example 4-2, 80 ml of propylene glycol monomethyl ether acetate (PGMEA) was dissolved in a flask and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 5.0 g of vinyl ether X-1 obtained in Synthesis Example 4-1 and 35 mg of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour and triethylamine was added. Then the reaction was completed. Ethyl acetate was added to the reaction solution, which was further washed with water, and then distilled under reduced pressure to remove ethyl acetate, water, and azeotrope PG.
MEA was distilled off to obtain an alkali-soluble resin (resin 4) having a substituent according to the present invention according to the present invention. The weight average molecular weight of the obtained resin was 11,000.

(5) Synthesis of Resin 5 60 mol% P-hydroxystyrene / 40 mol% acrylic acid-t-Bu copolymer resin manufactured by Triquest was used. The weight average molecular weight was 8500.

(6) Synthesis of Resin 6 (Synthesis Example 6-1) p which was dehydrated and distilled and purified by a conventional method
51.9 g (0.32 mol) of acetoxystyrene monomer and 1-adamantan-1-yl-1-methacrylate
14.82 g (0.0565 mol) of methyl ethyl was dissolved in 150 mL of tetrahydrofuran. Azobisisobutyronitrile (AI) at 80 ° C under nitrogen stream and stirring
The polymerization reaction was carried out by adding 1 g of BN) three times at intervals of 2.5 hours, and finally continuing stirring for another 5 hours. The reaction liquid was poured into 1500 mL of hexane to precipitate a white resin. After drying the obtained resin, tetrahydrofuran 2
It was dissolved in 00 mL. 4N hydrochloric acid was added to this, and the mixture was heated under reflux for 6 hours for hydrolysis, and then reprecipitated in 5 L of ultrapure water, and the resin was separated by filtration, washed with water, and dried. Further, the procedure of dissolving in 200 mL of tetrahydrofuran, dropping into 5 L of ultrapure water with vigorous stirring, and reprecipitating was repeated 3 times. The obtained resin was dried in a vacuum drier at 120 ° C. for 12 hours, and hydroxystyrene / 1-adamantan-1-yl-1-methylethyl copolymer resin R-6 was prepared.
Got When the copolymerization ratio was confirmed by 13 C-NMR,
It was 14/86. (Synthesis example 6-2) Resin R-6 obtained in synthesis example 6-1
20 g was dissolved in PGMEA (80 g) in a flask,
Vacuum distillation was performed to azeotropically distill off water and PGMEA. After confirming that the water content was sufficiently low, ethyl vinyl ether (2.5 g) and p-toluenesulfonic acid (0.00
2 g) was added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (0.003 g) was added to the reaction solution to stop the reaction, 80 mL of water and 200 mL of ethyl acetate were added, and the layers were separated.
After further washing with water, distilling off under reduced pressure, ethyl acetate, water, PG
MEA was distilled off to obtain a resin (resin 6) (30% by weight PGMEA solution) having a substituent relating to the present invention. 1H
When the introduced amount of ethyl acetal group was confirmed by -NMR, 15% of the hydroxyl groups of hydroxystyrene were protected. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 9800 and the dispersity was 1.82 by GPC measurement based on polystyrene.

(7) Synthesis of Resin 7 (Synthesis Example 7-1) 20 g of polyhydroxystyrene (VP8000) manufactured by Nippon Soda Co., Ltd. was dissolved in propylene glycol monomethyl ether acetate (PGMEA) (80 g) in a flask and distilled under reduced pressure. Do water and PGMEA
Was distilled off azeotropically. After confirming that the water content was sufficiently low, ethyl vinyl ether (2.5 g) and p-toluenesulfonic acid (0.002 g) were added, and the mixture was stirred at room temperature for 1 hr. Triethylamine (0.003 g) was added to the reaction solution to stop the reaction, and 80 mL of water and 200 m of ethyl acetate were added.
L was added, the mixture was separated, washed with water, and then distilled under reduced pressure to remove ethyl acetate, water, and PGMEA.
Wt% PGMEA solution) was obtained. When the introduced amount of the ethyl acetal group was confirmed by 1 H-NMR, 20% of the hydroxyl groups of hydroxystyrene were protected. (Synthesis Example 7-2) 1-Adamantyl-1-methylethanol was mixed with ethyl vinyl ether, mercury acetate was added thereto, and the mixture was stirred at room temperature for 12 hours. After extraction with ethyl acetate and water, washing with water, and evaporation under reduced pressure, 1-adamantyl-1-methylethylethyl vinyl ether (X-
2) was obtained. (Synthesis Example 7-3) Resin R-7 obtained in Synthesis Example 7-1
20 g was dissolved in propylene glycol monomethyl ether acetate (PGMEA) (80 g) in a flask and vacuum distillation was performed to distill off water and PGMEA azeotropically.
After confirming that the water content was sufficiently low, Synthesis Example 7-2
The vinyl ether X-2 (4.0 g) obtained in 1. and p-toluenesulfonic acid (0.0025 g) were added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (0.00
6 g) was added to stop the reaction, 80 mL of water and 200 mL of ethyl acetate were added, the mixture was separated, washed with water, and then distilled under reduced pressure to distill off ethyl acetate, water and PGMEA to have a substituent related to the present invention. A resin (resin 7) was obtained. The weight average molecular weight (Mw) of the obtained polymer was 10200 and the dispersity was 1.12.

(8) Synthesis of Resin 8 Instead of using the resin R-7 obtained in Synthesis Example 7-1,
Nippon Soda Polyhydroxystyrene (VP8000)
Resin 8 was synthesized by the method of Synthesis Examples 7-2 and 7-3, except that was used.

The structures of the above resins 1 to 8 are shown below.
The ratio of the repeating units in the resin shown below is shown by a molar ratio.

[0148]

[Chemical 40]

[0149]

[Chemical 41]

Synthesis Example 2 [Synthesis Example of Photo-Acid Generator] (1) (Synthesis of PAG1) PAG1 is described in Example 8 of JP-A-2000-314956.
The compound described in 6 was used. (2) (Synthesis of PAG2) As PAG2, the compound described in Example 9 of JP-T 2000-517067 was used.

(3) (Synthesis of triphenylsulfonium acetate (onium salt 1)) 20 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, and 12.5 g of silver (I) oxide was added thereto, and the mixture was stirred at room temperature for 4 hours. It was stirred. The reaction solution was filtered to remove the silver compound, and then 4.0 g of acetic acid was added to the filtrate. The solution was concentrated and the resulting oily substance was added to diisopropyl ether 3
After washing twice with 00 ml, 11.2 g of the desired product was obtained.

(4) (Synthesis of diphenyliodonium n-butyrate (onium salt 2)) 50 g of (diphenyliodonium) iodide was dissolved in 2 liters of methanol, 22 g of silver oxide (I) was added thereto, and the mixture was stirred at room temperature for 4 hours. It was stirred. After the reaction solution was filtered to remove the silver compound, 7.5 g of n-butyric acid was added to the filtrate.
The solution was concentrated, and the obtained solid was washed with 300 ml of diisopropyl ether to obtain 32 g of the desired product.

The structures of the above PAG1 and PAG2 and onium salts 1 and 2 are shown below.

[0154]

[Chemical 42]

Examples 1 to 12 and Comparative Examples 1 to 4 The components shown in Table 1 were dissolved in PGMEA solvent in a weight ratio shown in Table 1 so that the total weight ratio was 16%.
A positive photoresist was prepared by filtering with a 1 μm microfilter. Using a spin coater (Mark8 manufactured by Tokyo Electron), the obtained resist solution was coated on a silicon wafer on which a 110 nm coating film was formed with organic BARC (DUV42) manufactured by Nissan Kagaku Co., Ltd., and dried at 120 ° C. for 90 seconds. A resist film having a thickness of 0.6 μm was formed. FPA-3000 manufactured by Canon through the resist film through a mask
With KrF excimer laser light using EX5 (wavelength 24
8 nm, NA 0.60, 1/2 annular zone illumination) pattern exposure. After exposure, heat treatment at 110 ℃ for 90 seconds,
Development was performed with a 2.38 wt% TMAH aqueous solution, followed by rinsing and spin drying to obtain a resist pattern.

(Evaluation Method of Line Edge Roughness) Du
At an exposure amount such that the line and space size of the mask size 1.0 μm with a ty ratio of 1: 1 is 0.20 μm, the line width of the isolated line of 0.18 μm is manufactured by Hitachi, Ltd. SEM: S- The line edge roughness was 3 times the standard deviation of the values measured at 50 points by 8840.

(Evaluation Method of PED Stability) The line size of the mask size 1.0 μm with the duty ratio of 1: 1 is 0.2.
At the exposure amount of 0 μm, PEB is immediately obtained after the exposure.
Line dimension (CD (0h)) on the processed wafer,
Line dimension CD on PEB processed wafer after 2 hours
(2h) is manufactured by Hitachi, Ltd., measuring SEM: S-884
Measured by 0, | CD (2h) -CD (0h) | / C
D (0h) was used as an index of PED stability. The results are shown in Table 1 below.

[0158]

[Table 1]

The structure of PAG3 used in Table 1 is shown below.

[0160]

[Chemical 43]

In all resists of Examples 1 to 12 and Comparative Examples 1 to 4, 0.1 part by weight of the following compound (a) was used as an additive.

[0162]

[Chemical 44]

As shown in Table 1 above, it can be seen that the composition of the present invention is superior in line edge roughness and PED stability as compared with the comparative example.

Examples 13 to 19, Reference Examples 1 and 2, and Comparative Example 5 The components shown in Table 2 were dissolved in PGMEA solvent in a weight ratio shown in Table 2 so that the total weight ratio was 16%. Then, it was filtered through a 0.1 μm microfilter to prepare a positive photoresist. Each component in Table 2 is shown in Table 1.
The same as in. In addition, in Example 19 and Comparative Example 5, 0.1% of the compound (a) was used as an additive.
Used by weight.

Using a spin coater (Mark8 manufactured by Tokyo Electron), the obtained resist solution was coated on a silicon wafer on which 110 nm of organic BARC (DUV42) manufactured by Nissan Chemical Co., Ltd. was formed, and dried at 120 ° C. for 90 seconds. Then, a resist film having a thickness of 0.6 μm was formed. Canon FPA-3000EX through the resist film through a mask
With KrF excimer laser light (wavelength 248n
m, NA 0.60, 1/2 annular illumination) pattern exposure was performed. After the exposure, heat treatment is performed at 110 ° C. for 90 seconds, and 2.
After development with a 38 wt% TMAH aqueous solution, followed by rinsing,
Spin drying was performed to obtain a resist pattern.

(Evaluation Method of Line Edge Roughness and PED Stability) The same method as in the above Examples and Comparative Examples was used. (Evaluation Method of Sensitivity) The sensitivity was defined as the exposure amount at which the line-and-space dimension of the mask size 1.0 μm with the duty ratio 1: 1 was 0.20 μm. The results are shown in Table 2.

[0167]

[Table 2]

From the results shown in Table 2, as the resin (a), a repeating unit having a group represented by the general formula (X), a repeating unit having a group represented by the general formula (Y1) and a general formula ( It can be seen that the resist composition containing a resin having at least one of the repeating units having a group represented by Y2) is excellent in line edge roughness, PED stability, and sensitivity.

[0169]

According to the present invention, a chemically amplified positive photoresist composition excellent in line edge roughness and PED stability, and a chemically amplified positive photoresist composition excellent in sensitivity are provided. .

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA03 AA04 AB16 AC04                       AC08 AD03 BE00 BE07 BE10                       BG00 CB14 CB17 CB41 FA17

Claims (2)

[Claims] 1. A resin that is decomposed by the action of an acid to increase its solubility in an alkali developing solution, and (b) An acid is generated by irradiation with an actinic ray or radiation represented by the following general formula (1). A positive photoresist, containing a compound and at least one selected from the group of compounds that generate an acid upon irradiation with actinic rays or radiation represented by the following general formulas (2) to (4). Composition. [Chemical 1] In formula (1), R ₁ and R ₂ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a cyano group. R ₁ and R ₂ may combine to form a ring. R ₃ represents an alkyl group or an aryl group. R ₁ and R ₂ may be bonded to R ₁ or R ₂ of another compound represented by the general formula (1) via a single bond or a linking group. [Chemical 2] In general formulas (2) to (4), R _{11 to} R ₁₉ are each independently
It represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group. X ⁻ represents a hydroxide anion or a carboxylic acid anion having a molecular weight of 100 or less. 2. The resin (a) is represented by a repeating unit having a group represented by the general formula (X), and a repeating unit having a group represented by the general formula (Y1) and a general formula (Y2). The positive photoresist composition according to claim 1, which is a resin having at least one of a repeating unit having a group. [Chemical 3] In formula (X), R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group. Z represents an alkyl group. m is 1
Represents an integer of 20. [Chemical 4] In the general formula (Y1), R ₂₀ represents an alkyl group. In the general formula (Y2), R ₂₁ and R ₂₂ are each independently
Represents an alkyl group.