KR100692264B1 - Positive radiation-sensitive resin composition - Google Patents

Abstract

The present invention particularly provides a chemically amplified positive photoresist composition that exhibits high sensitivity and high resolution and exhibits good halftone retardation shift mask titration and side lobe resistance that are incompatible with conventionally. The purpose.

According to the present invention, a positive radiation containing a polymer decomposed by the action of an acid and increasing in solubility in an alkaline developer, a compound which generates an acid by irradiation with actinic radiation or radiation, and an acetal compound having a specific structure A resin composition is provided.

Description

Positive radiation sensitive resin composition {POSITIVE RADIATION-SENSITIVE RESIN COMPOSITION}

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

As positive type photoresist compositions, chemically amplified resist compositions are described in US Pat. No. 4,491,628, European Patent No. 29,139, and the like. In the chemically amplified positive resist composition, an acid is generated in the exposed portion by irradiation with radiation such as far ultraviolet rays, and the solubility of the active radiation in the developer and the non-irradiated portion is changed by the reaction using the acid as a catalyst. To form a pattern on a substrate.

As such an example, a combination of a compound which produces an acid by photolysis with an acetal or O, an N-acetal compound (see Japanese Patent Application Laid-Open No. 48-89003), an olso ester or an amide acetal compound (Japanese Patent Laid-Open No. 51-120714) Publications), combinations with polymers having acetal or ketal groups in the main chain (Japanese Patent Publication No. 53-133429), combinations with enol ether compounds (Japanese Patent Publication No. 55-12995), combinations with N-acylimino carbonate compounds ( Japanese Patent Application Laid-Open No. 55-126236), a combination with a polymer having an olso ester group in the main chain (Japanese Patent Application Laid-Open No. 56-17345), a combination with a tertiary alkyl ester compound (Japanese Patent Application Laid-Open No. 60-3625), or a cyryl ester compound Combinations (Patent No. 60-10247), and combinations with a Cyryl ether compound (Patent No. 60-37549, Pat. No. 60-121446) and the like. They show high photosensitivity in principle because their quantum yields exceed one.

Similarly, at room temperature, stability is shown with time, but in the presence of acid, it is a system which decomposes by heating and alkali solubilizes, for example, in Japanese Patent Application Laid-Open Nos. 59-45439, 60-3625, and 62-229242. JP 63-27829, JP 63-36240, JP 63-250642, Polym. Eng. Sce., Vol. 23, p. 12 (1983); ACS. Sym. 242, page 11 (1984); Semiconductor World, November 1987, page 91; Macromolecules, 21, 1475 pages (1988); Acid-producing compounds by exposure described in SPIE, 920, page 42 (1988), etc., esters or carbonate ester compounds of tertiary or secondary carbon (e.g., t-butyl, 2-cyclohexenyl); The combination system of is mentioned. These systems also have high sensitivity and have a low absorption in the deep-UV region compared with the naphthoquinone diazide / novolak resin system, and thus can be an effective system for shortening the light source.

Japanese Patent Application Laid-Open No. Hei 2-19847 discloses a photoresist composition comprising a resin in which a phenolic hydroxy group of poly (p-hydroxystyrene) is protected in whole or in part by a tetrahydropyranyl group.

Similarly, Japanese Patent Application Laid-Open No. 4-219757 discloses a photoresist composition characterized in that 20 to 70% of the phenolic hydroxy groups of poly (p-hydroxystyrene) contain a resin substituted with an acetal group.

In addition, Japanese Patent Application Laid-Open No. 5-249682 discloses a photoresist composition using a resin which is similarly protected with acetal.

In addition, Japanese Patent Application Laid-Open No. 8-123032 discloses a photoresist composition using a ternary copolymer containing a group substituted with an acetal group.

Furthermore, Japanese Patent Application Laid-Open Nos. 5-113667, 6-266112, 6-289608, and 7-209868 disclose photoresist compositions composed of hydroxystyrene and a (meth) acrylate copolymer. Is disclosed.

Japanese Patent Application Laid-Open No. 9-297396 discloses acetalizing hydrogen atoms of phenolic hydroxyl groups in a polymer having a group decomposable by an acid, a radiation sensitive acid generator, and a compound having a molecular weight of less than 1000 having a phenolic hydroxyl group. A radiation sensitive resin composition containing a compound and an acid diffusion control material is described. It is described that this composition is excellent in the resolution, cross-sectional shape, and focus tolerance of a contact hole.

On the other hand, various tests have been tried to further increase the resolution by super-resolution techniques such as exposure technique or mask technique. In addition, in the super resolution technology, various super resolution technologies are being studied on each of a light source surface, a mask surface, a copper surface, and a screen. In the light source surface, there is a technique of increasing the resolution by setting a light source called a strain irradiation method, that is, a shape different from a conventional circular shape. On the mask surface, a technique has been reported in which a phase shift mask is used to control the phase, that is, to give a phase difference to light passing through the mask, and to use the interference well to obtain high resolution (e.g. Optics (1) to (4), phototechnical contact, vol. 27, No. 12, 762 (1988), vol. 28, No. 1, 59 (1990), vol. 28, No. 2, 108 (1990) , vol. 28, No. 3, 165 (1990), Japanese Patent Application Laid-Open No. 58-173744, Japanese Patent Application No. 62-50811, Japanese Patent Application No. 62-67514, Japanese Patent Application Laid-Open No. 1-147458, Japanese Patent Application Laid-Open No. 1-283925, Japanese Patent Laid-Open No. 2-211451, etc.).

In addition, as described in Japanese Patent Application Laid-Open No. Hei 8-15851, although the resist exposure method using the halftone system phase shift mask is attracting particular attention as a practical technique for improving the spatial and contrast of the projected image, it is transferred to the resist. In the light intensity distribution of the exposure light, so-called sub-peaks having different main peaks are generated and are exposed to a portion that should not be originally exposed. In particular, the higher the interference σ, the larger the sub-peak. When such a sub peak occurs, uneven portions due to the sub peak are formed in the resist after exposure and development in the positive resist.

Until now, in the prior art of the resist material mentioned above, since the uneven part generate | occur | produces after image development due to these sub peaks (side lobe light), the improvement is desired.

In the case of using the super resolution technology, the resolution is improved, but other resist characteristics may be lowered. Therefore, it is not known in the art how to design a positive photoresist material, for example, when using a super resolution technique.

An object of the present invention is to provide a chemically amplified positive resist composition which exhibits high sensitivity and high resolution, in particular, having good halftone phase shift shift mask titration (sirobe light resistance) which is not compatible in the prior art. To provide.

As a result of thorough examination in view of such a phenomenon, the inventors have found a positive photoresist composition containing at least a binder having an acid-decomposable group, a compound which generates an acid by irradiation with actinic light or radiation, and an acetal compound having a specific structure. The present invention has been completed in view of achieving the above object of the present invention.

That is, the positive radiation sensitive resin composition which concerns on this invention consists of the following structures.

(1) The polymer (a) which decomposes by the action of an acid, and the solubility to an alkaline developing solution increases, the compound (b) which generate | occur | produces an acid by irradiation of actinic light or a radiation, and following General formula (A) or The positive radiation sensitive resin composition containing at least 1 sort (s) of the acetal compound (c) represented by General formula (B):

(In formula (A) or (B), R <_1> and R <_2> respectively independently has a linear, branched, or cyclic C1-C12 substituent, or the C7-C18 substituent. Aralkyl group may be used).

(2) The polymer (a) is a polymer obtained by reacting an alkali-soluble polymer having a hydroxyl group with a vinyl ether compound represented by the following general formula (C) and an alcohol compound represented by the following general formula (D) under an acid catalyst. The positive radiation sensitive resin composition as described in said (1) which makes it:

(In formula (C) or formula (D), each of R ₃ or R ₄ has an alkyl group which may have a linear, branched or cyclic C 1-12 substituent, and a C 6-18 substituent. Or an aralkyl group which may have an aromatic group or a substituent having 7 to 18 carbon atoms).

(3) Positive type as described in said (1) or (2) characterized by the total amount of said acetal compound (c) being 0.1 weight part or more and less than 100 weight part with respect to 100 weight part of solid content of the said polymer (a). Radiation-sensitive resin composition.

The present invention will be described in detail below.

Acetal compound (c)

Component (c) of this invention is a compound represented by general formula (A) and / or general formula (B).

R ₁ and R ₂ are each independently a linear, branched or cyclic unsubstituted or substituted alkyl group having less than 1 to 12 carbon atoms, or an aral which may have an unsubstituted or substituted group having 7 to 18 carbon atoms. It's a killer.

Examples of the linear, branched or cyclic C1-C12 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group and 2-ethyl Alkyl groups, such as a hexyl group, an octyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and 1-adamantyl ethyl group, are mentioned.

As other substituents such as these alkyl groups, cycloalkyl groups and aryls which may contain hydroxyl atoms, halogen atoms such as fluorine, chlorine, bromine and iodine, amino groups, nitro groups, cyano groups, carbonyl groups, ester groups, alkoxy groups and heteroatoms The substituent which has a hydroxy group and a sulfonyl group is mentioned. As the carbonyl group, an alkyl substituted carbonyl group and an aromatic substituted carbonyl group are preferable, and as an ester group, an alkyl substituted ester group and an aromatic substituted ester group are preferable, and an alkoxy group is a methoxy group, an ethoxy group, a propoxy group and t-butoxy group. desirable. As a cycloalkyl group, a cyclohexyl group, an adamantyl group, a cyclopentyl group, a cyclopropyl group, etc. are mentioned, for example, As a hetero atom, an oxoranyl group etc. are mentioned. A phenoxy etc. are mentioned as an aryloxy group, You may have a substituent in this aryl group. Examples of the substituent having a sulfonyl group include alkylsulfonyl groups such as methylsulfonyl group and ethylsulfonyl group, and arylsulfonyl groups such as phenylsulfonyl group.

As an aralkyl group, a benzyl group, a phenethyl group, benzhydryl group, a naphthyl methyl group, etc. are mentioned. In these aralkyl groups, what was described by the other substituent of an alkyl group can be hold | maintained as a substituent.

As a synthesis method of the said acetal compound, it can synthesize | combine by dissolving a vinyl ether compound and a corresponding alcohol compound in a suitable solvent, and making it react in presence of an acidic catalyst. Here, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, etc. can be used as an acid catalyst.

The reaction is accompanied by an acetal exchange reaction and is obtained as a mixture of a plurality of acetal compounds. The reaction can be suitably used for the purpose of the present invention, either alone or as a mixture.

As a vinyl ether compound and an alcohol compound, it can represent with general formula (C) and general formula (D), respectively.

Hereinafter, the example of the acetal compound (c) used suitably for this invention is shown. In the following specific examples, Me represents a methyl group, t-Bu represents a t-butyl group, and iso-Bu represents an isobutyl group.

It is preferable that the acetal compound (c) which is an essential component of this invention is 0.1 weight part or more and less than 100 weight part with respect to 100 weight part of solid content of a polymer (a). More preferably, it is 1 weight part or more and less than 50 weight part, Especially preferably, it is 2 weight part or more and less than 30 weight part. If it exceeds 100 parts by weight, it is not preferable because of the tendency of the heat resistance of the resist to decrease, and if it is less than 0.1 part by weight, the effect of the present invention may not be expressed.

 (a) A polymer that decomposes under the action of an acid and increases solubility in an alkaline developer (called an acid-decomposable polymer).

An acid-decomposable polymer is a polymer which is decomposed by an acid generated from a photoacid generator by irradiation of actinic light or radiation and solubilized in an alkaline developer. An acid-decomposable polymer is a polymer which protected the alkali-soluble group of the trunk polymer which has an alkali-soluble group with the group which decomposes by the action of an acid. As an alkali-soluble group, a phenolic hydroxyl group and a carboxylic acid group are preferable. As a protecting group of this alkali-soluble group, an acetal group, a ketal group, t-butyl ester group, t-butoxycarbonyl group, etc. are preferable, an acetal group and a t-butyl ester group are more preferable, an acetal group is especially a sensitivity and after exposure It is preferable from the viewpoint of sensitivity fluctuation with respect to standing time and stability of dimensional fluctuation (PED).

As the trunk polymer, hydroxystyrenes are preferable, and copolymers with acid-decomposable (meth) acrylates such as t-butyl acrylate or t-butyl methacrylate can be used. Moreover, a non-acid-decomposable group can be introduce | transduced in order to prepare the alkali solubility of trunk polymer. As a method of introducing a non-acid-decomposable group, a method by copolymerization with styrenes, (meth) acrylic acid esters, (meth) acrylic acid amides, or a method of protecting the hydroxyl group of hydroxystyrene with a non-acid-decomposable substituent is preferable. Do. As a substituent of a non-acid-decomposable group, although an acetyl group, a mesyl group, a toluenesulfonyl group, etc. are preferable, it is not limited to these.

The polymer represented by general formula (E) as an acid-decomposable polymer below is preferable.

In formula (E), R <_3> represents a hydrogen atom or a methyl group, and each of some R <_3> may be same or different.

R ₄ is an alkyl group which may have a linear, branched or cyclic C1-C12 substituent, an aromatic group which may have a C6-C18 substituent, or an aral which may have a C7-C18 substituent Indicates a kill group. Here, as an example of an alkyl group and an aralkyl group, the thing similar to the example described in R <_1> , R <_2> of the said General formula (A) or (B) is mentioned.

As an aromatic group, a benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, etc. are mentioned. In this aromatic ring phase, what was described by the other substituent of the said alkyl group can hold as a substituent.

R ₅ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a t-butyl group), an acetyl group, a mesyl group, a tosyl group, and the like. An acetyl group is more preferable.

R ₆ represents a hydrogen atom, a linear, branched or cyclic C 1-8 alkyl group, an aromatic group which may have 6 to 12 carbon atoms or an aralkyl group which may have 7 to 18 carbon atoms substituents. .

R ₇ and R ₈ are each independently a hydrogen atom, a linear, branched or cyclic C 1-8 alkyl group, an aromatic group which may have 6 to 12 carbon atoms, or a 7 to 18 carbon atoms substituent. Also shows a good aralkyl group.

In R <_6> -R <_8> , as an example of an alkyl group, an aromatic group, and an aralkyl group, the example described in R <_1> , R <_2> of the said General formula (A) or (B), and the example of said R <_3> , R <_4> The example in the range of the said carbon number is mentioned.

a, b, c, d and e each represent% of each monomer unit individually, 0 <a / (a + b) <0.6 is preferable, and 0.05 <a / (a + b) <0.5 is more preferable. Do. Moreover, 0 <= c / (a + b + c) <0.3 is preferable, and 0 <= c / (a + b + c) <0.2 is more preferable. Moreover, 0 <= d / (a + b + d) <0.4 is preferable and 0 <= d / (a + b + d) <0.3 is more preferable. Moreover, 0 <= e / (a + b + e) <0.4 is preferable and 0 <= e / (a + b + e) <0.3 is more preferable.

The preferable example of an acid-decomposable polymer is shown below. However, "i-Bu" represents an isobutyl group, "n-Bu" represents an n-butyl group, and "Et" represents an ethyl group.

The weight average molecular weight of the said polymer (a) can be measured by gel permeation chromatography (GPC) as polystyrene conversion molecular weight (Mw), Preferably it is 2,000-200,000, 4,000-50,000 are more preferable, 8,000 30,000 is particularly preferred. When the molecular weight exceeds 200,000, the solubility is weakened and the resolution tends to decrease.

Moreover, the said polymer (a) can be used in combination of 2 or more types.

The polymer (a) used in the present invention can be obtained by acetalizing a part of the phenolic hydroxyl group of the trunk polymer having a phenolic hydroxyl group by using the corresponding vinyl ether compound and an acid catalyst.

For example, an acetal group can be introduce | transduced by the method of Unexamined-Japanese-Patent No. 5-249682, 8-123032, and 10-221854.

In addition, it is possible to introduce a desired acetal group using the acetal exchange reaction of S. Malik described in J. Photopolym. Sci. Tech., 11 (3) 431 (1998). As shown in the following reaction formula, R ₃ reacts a resin having a phenolic hydroxyl group with a vinyl ether compound represented by the general formula (C) and an alcohol compound represented by the general formula (D) in the presence of an acid catalyst. And only R ₄ or R ₄ can be introduced as an acetal group as represented by the following general formula (F).

In this invention, as addition amount in the composition of the said polymer (a), Preferably it is 40 to 99 weight% with respect to solid content total weight of a composition, More preferably, it is 60 to 97 weight%.

In this invention, alkali-soluble resin which does not contain an acid-decomposable group in a positive radiation sensitive resin composition can be used, and a sensitivity improves by this. Alkali-soluble resin which does not contain the said acid-decomposable group (henceforth simply alkali-soluble resin) is resin which is soluble in alkali, and polyhydroxy styrene, a novolak resin, and derivatives thereof are mentioned as a preferable thing. Moreover, the copolymerization resin containing a p-hydroxy styrene unit can also be used if it is alkali-soluble.

Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p- / o-hydroxystyrene) copolymer, poly (p-hydroxystyrene / styrene) Copolymers are preferably used. Furthermore, poly (alkyl substituted hydroxystyrene) resins such as poly (4-hydroxy-3-methylstyrene), poly (4-hydroxy-3,5-dimethylstyrene), and some of the phenolic hydroxyl groups of the resin Alkylated or acetylated resins are also preferably used if they are alkali soluble.

Moreover, when a part of phenol nucleus (30 mol% or less of all the phenol nuclei) of the said resin is hydrogenated, transparency of resin improves and it is preferable at the point of the sensitivity, resolution, and profile formation of a rectangle.

In this invention, as addition amount in the composition of alkali-soluble resin which does not contain the said acid-decomposable group, Preferably it is 2-60 weight% with respect to the total weight of solid content of a composition, More preferably, it is 5-30 weight% to be.

 (b) Compounds which generate an acid by irradiation of actinic light or radiation (called photoacid generators)

Examples of the photoacid generator used in the present invention include photoinitiators of photocationic polymerization, photoinitiators of radical photopolymerization, photochromic agents of pigments, photochromic agents, microresists, and the like. , Particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and an acid-producing compound and mixtures thereof. have.

Moreover, as a compound which generate | occur | produces an acid by irradiation of actinic light or radiation used in this invention other than this, for example, a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, a sulfonium salt, a selenium salt, an arzonium salt Compounds that generate sulfonic acid by photolysis such as onium salts, organohalogen compounds, organometallic / organohalides, photoacid generators with o-nitrobenzyl-type protecting groups, iminosulfonates, disulfone compounds, diazos Ketosulfone, a diazo disulfone compound, etc. are mentioned.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by these light in the main chain or side chain of a polymer can be used.

Furthermore, VNRPillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc., (C), 329 ( 1970), US Pat. No. 3,779,778, European Patent No. 126,712 and the like can also be used compounds that generate acid by light.

Among the compounds generating an acid by decomposition by irradiation with the above-mentioned actinic light or radiation, what is particularly effectively used will be described below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalogen methyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds are specifically mentioned, It is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or a sulfonium salt represented by general formula (PAG4).

Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group.

Z ^- represents an anion pair is, for example, _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, a pentafluoro- Condensed polynuclear aromatic sulfonic acid anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes and the like, such as robenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion, may be mentioned, but not limited thereto.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ , and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Although the compound shown below is mentioned specifically, it is not limited to these.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and are known, for example, from JWKnapczyk et al, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok et al, J. Org. Chem., 35 , 2532 (1970), E. Goethas etal, Bull. Soc. Chem. Belg., 73, 546, (1964), HM Leicester, J. Ame. Chem. Soc., 51, 3587 (1929), J. V. Crivello et al, J. Polym. Chem. Ed., 18,2677 (1980), US Pat. No. 2,807,648, US Pat. No. 4,247,473, Japanese Patent Application Laid-Open No. 53-101,331 and the like.

(3) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is mentioned specifically, it is not limited to these.

(4) Diazodisulfone derivative represented by the following general formula (PAG7).

R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted.

Although the compound shown below is mentioned specifically, it is not limited to these.

The addition amount of the compound which decomposes | disassembles by irradiation of these actinic rays or radiation is used normally in 0.001-40 weight% based on solid content in a composition, Preferably it is 0.01-20 weight%, More preferably Preferably it is used in the range of 0.1 to 5% by weight. If the amount of the compound that decomposes by irradiation of actinic radiation or radiation to generate an acid is less than 0.001% by weight, the sensitivity is lowered. If the amount is more than 40% by weight, the light absorption of the resist becomes too high. (Burning process in particular) The margin is narrowed, which is undesirable.

(Other components used in the present invention)

The positive radiation-sensitive resin composition of the present invention further contains an acid-decomposable dissolution promoting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic base compound, and a compound for promoting solubility in a developing solution, if necessary. You can do it.

The positive radiation-sensitive resin composition of the present invention may contain a fluorine-based and / or silicon-based surfactant (surfactant containing both a fluorine-based surfactant, a silicon-based surfactant and a fluorine atom, and a silicon atom).

As these surfactants, for example, Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application No. 61-226746, Japanese Patent Application No. 61-226745, Japanese Patent Application No. 62-170950, Japanese Patent Application No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165 The surfactant of 8-62834, Unexamined-Japanese-Patent No. 9-54432, and Unexamined-Japanese-Patent No. 9-5988 is mentioned, The following commercially available surfactant can also be used as it is.

As a commercially available surfactant which can be used, For example, F-Top EF301, EF303 (made by Shinjuku Co., Ltd.), Floroid FC430, 431 (made by Juus Reem Co., Ltd.), Megapack F171, F173, F176, F189, And fluorine-based surfactants or silicone-based surfactants such as R08 (manufactured by Japan Nippon Ink Co., Ltd.) and Suflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Ukcho Co., Ltd.). Moreover, polysiloxane polymer-KP-341 (made by Shinwol Chemical Co., Ltd.) can also be used as a silicone type surfactant.

The compounding quantity of surfactant is 0.01 weight%-2 weight% normally with respect to 100 weight part of solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%.

These surfactant can be used individually by 1 type or in combination of 2 or more types.

Organic basic compounds may be used in the compositions of the present invention. This is preferable because it improves the stability at the time of preservation and the change in goodness due to the PED.

Preferred organobasic compounds that can be used in the present invention are compounds which are more basic than phenol. Especially, basic compound containing nitrogen is preferable.

As a preferable chemical environment, the following formula (A)-(E) structure is mentioned.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different, and may be a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aminoalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms, or 6 to 20 carbon atoms. Is a substituted or unsubstituted aryl group, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

(In formula, R <^253> , R <^254> , R <^255> and R <^256> may be same or different, and represents a C1-C6 alkyl group.)

Further preferred compounds are nitrogen-containing cyclic compounds or nitrogen-containing basic compounds having two or more nitrogen atoms in different chemical environments in one molecule.

As a nitrogen-containing cyclic compound, it is more preferable that it is polycyclic structure. As a preferable specific example of a nitrogen-containing polycyclic cyclic compound, the compound represented by the following general formula (F) is mentioned.

In formula (F), Y and Z respectively independently represent the linear, branched, and cyclic alkylene group which may contain the hetero atom and may be substituted.

Here, the hetero atom may be a nitrogen atom, a sulfur atom, or an oxygen atom. As an alkylene group, C2-C10 is preferable, More preferably, it is 2-5. As a substituent of an alkylene group, a halogen atom and a halogen substituted alkyl group other than a C1-C6 alkyl group, an aryl group, and an alkenyl group are mentioned. Moreover, the compound shown below is mentioned as a specific example of a compound represented by general formula (F).

Among them, 1,8-diazabicyclo [5. 4. 0] undeca-7-ene, 1,5-diazabicyclo [4. 3. 0] nona-5-ene is particularly preferred.

As the nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, particularly preferably, a compound or alkylamino group containing both a substituted or unsubstituted amino group and a ring structure containing nitrogen atoms Compound. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethyl Aminopyridine, 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-aminomorphol , N- (2- aminoethyl) morpholine, trimethylamine, and the like are imidazole, triphenyl imidazole, methyl-diphenyl-imidazole, but not limited to these.

These nitrogen-containing basic compounds are used alone or in combination of two or more thereof. The usage-amount of a nitrogen-containing basic compound is 0.001-10 weight part normally with respect to 100 weight part of compositions (excluding a solvent), Preferably it is 0.01-5 weight part. If it is less than 0.001 weight part, the said effect will not be acquired. On the other hand, when it exceeds 10 weight part, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

The dissolution promoting compound for the developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less having two or more phenolic OH groups or one or more carboxyl groups. In the case of having a carboxyl group, an alicyclic or aliphatic compound is preferable for the same reasons as described above. The preferable addition amount of this dissolution promoting compound is 2-50 weight% with respect to the polymer of this invention, More preferably, it is 5-30 weight%. At an added amount exceeding 50% by weight, the development residue deteriorates, and a new disadvantage of deforming the pattern during development occurs, which is not preferable.

Such phenolic compounds having a molecular weight of 1000 or less can be easily synthesized by those skilled in the art, for example, referring to methods described in Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Pat. .

Although the specific example of a phenol compound is shown below, the compound which can be used by this invention is not limited to these.

Resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5'- Hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phloroglucoxide, 2,4,2 ', 4'-biphenylterol, 4,4'-thiobis (1,3-dihydroxy) Benzene, 2,2 ', 4,4'-tetrahydroxydiphenylether, 2,2', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2 ', 4,4'-tetrahydroxy Cddiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ', α "- Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ', α "-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,2 , 2-tris- (hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl ) Hexane, 1,2-tetrakis (4-hydroxyphenyl) , 1,1,3-tris (hydroxyphenyl) butane and para [α, α, α ', α'- tetrakis (4-hydroxyphenyl)] - xylene and the like can be given.

Suitable dyes are oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above Orient Chemical Industries, Ltd.) Crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), and the like.

In order to improve the acid generation rate by exposure, a photosensitizer as listed below may be further added. Suitable photosensitizers include, in particular, benzophenone, p, p &apos; -tetramethyldiaminobenzophenone, p, p &apos; -tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxy Anthracene, anthracene, 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, Picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone , 1,2-naphthoquinone, 3,3 &apos; -carbonyl-bis (5,7-dimethoxycarbonylcoumarin), coronene, and the like, but are not limited thereto.

Moreover, these photosensitizers can also be used as a light absorber of the ultraviolet light of a light source. In this case, the light absorber reduces the reflected light from the substrate and exhibits the effect of standing wave improvement by reducing the influence of multiple reflections in the resist film.

The photosensitive composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. As a solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-meth Oxyethyl 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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

In this invention, surfactant other than the said fluorine type and / or silicone type surfactant can be added. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl Polyoxyethylene alkylaryl ethers such as phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tri Sorbitan fatty acid esters such as oleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triolee Eight, polyoxyethylene sorbitan tris Nonionic, such as polyoxyethylene sorbitan fatty acid esters, such as O-rate can be given a surface active agent or the like. The compounding quantity of these surfactant is 2 weight% or less normally with respect to 100 weight% of solid content in the composition of this invention, Preferably it is 1 weight% or less.

These surfactants may be added alone, or may be added in combination.

The composition is applied to a substrate (e.g., silicon / silicon dioxide coating) on which the composition is to be used for the manufacture of the precision integrated circuit device by a suitable coating method such as spinner, coater, etc., and then pre-bake. By exposing through a mask of, post-bake and developing, a good resist pattern can be obtained. Here, as exposure light, Preferably it is the far ultraviolet of the wavelength of 250 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), an X-ray, an electron beam, etc. are mentioned.

As a developing solution of the photosensitive composition of this invention, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 1st amines, such as ethylamine and n-propylamine, diethylamine, di second amines such as -n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as cyclic amines such as quaternary ammonium salts, pyrrole and piperidine can be used.

Moreover, alcohol and surfactant can be added to the alkaline aqueous solution in an appropriate amount.

(Example)

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example.

Synthesis Example 1

32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, stirred under a stream of nitrogen, and 0.033 g of azobis isobutylnitrile (AIBN) was added three times at three hours intervals at 83 ° C. The stirring was continued for 6 hours to carry out the polymerization reaction. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried and then dissolved in 150 ml of methanol.

An aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water was added thereto, and the mixture was hydrolyzed by heating under reflux for 3 hours. Thereafter, 200 ml of water was added thereto, diluted, and neutralized with hydrochloric acid to precipitate a white resin. This resin was filtered off, washed with water and dried. The solution was dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitation was carried out with vigorous stirring in 5 L of super distilled water. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain poly (p-hydroxystyrene) [resin R-1]. The weight average molecular weight of obtained resin was 13,000.

Synthesis Example 2

35.25 g (0.2 mole) of p-tert-butoxystyrene monomer and 5.21 g (0.05 mole) of styrene monomer which were dehydrated and distilled and purified by the conventional method were dissolved in 100 ml of tetrahydrofuran. 0.033 g of azobis isobutylnitrile (AIBN) was added three times at three-hour intervals at 83 ° C under nitrogen stream and with stirring, and the stirring was continued for six more hours at the end. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried and then dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added thereto and hydrolyzed by heating under reflux for 6 hours, followed by reprecipitation in 5 L of superdistilled water, and the resin was filtered off, washed with water and dried. Furthermore, it melt | dissolved in 200 ml of tetrahydrofuran, and it dripped at 5 L of super distilled water, stirring vigorously, and reprecipitated. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer [resin R-2]. The weight average molecular weight of obtained resin was 11,000.

Synthesis Example 3

40 g (0.33 mole) of p-hydroxystyrene and 10.7 g (0.08 mole) of tert-butyl acrylate were dissolved in 50 g of dioxane, and 8 g of azobis isobutyl nitrile (AIBN) was added thereto, followed by heating and stirring at 60 ° C. under nitrogen stream for 8 hours. Was performed. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried, dissolved in acetone, and dripped and reprecipitated while stirring vigorously in 5 L of super distilled water. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / tert-butylacrylate) copolymer [resin R-3]. The weight average molecular weight of obtained resin was 21,000.

Synthesis Example 4

After 24 g of poly (p-hydroxystyrene) Nippon Procurement Co., Ltd. (molecular weight 8,000) was dissolved in 100 ml of dioxane, bubbling was performed with nitrogen for 30 minutes. 13.1 g of di-tert-butyl-dicarbonates were added to this solution, and 36 g of triethylamines were dripped with stirring. After completion of the dropwise addition, the reaction solution was stirred for 5 hours. The reaction solution was added dropwise to an aqueous 1% by weight ammonia solution to precipitate a polymer. The obtained resin was dried, dissolved in acetone, and dripped and reprecipitated with 5 L of super distilled water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene) copolymer [resin R-4]. The weight average molecular weight of obtained resin was 8,300.

Synthesis Example 5

70 g of poly (p-hydroxystyrene) Japan Procurement Co., Ltd. (molecular weight: 8,000) was dissolved in 320 g of propylene glycol methyl ether acetate (PGMEA), 0.35 g of p-toluenesulfonic acid pyridinium salt was added, and the solution was dissolved at 60 ° C. It was. This liquid mixture was decompressed to 60 mmC and 20 mmHg, and about 40 g of solvent was distilled off together with the water remaining in the system. After cooling to 20 ° C, 18.9 g of benzyl alcohol was dissolved. Then, 17.5 g of tert- butyl vinyl ether was added, and it stirred at 20 degreeC for 5 hours. Moreover, 5.5 g of pyridine was added, 5.9 g of acetic anhydride was then added, and it stirred at 20 degreeC for 1 hour and 30 minutes. 280 ml of ethyl acetate was added to the reaction mixture, and 140 ml of water and 12 ml of acetone were further added for extraction. After the water washing operation was repeated three times, distillation was performed at 60 ° C. and 20 mm Hg to remove water in the system.

In addition, the obtained resin solution was diluted with acetone and precipitated in a large amount of hexane to obtain a white resin.

This operation was repeated three times, and the resultant resin was heated in a vacuum dryer at 40 ° C. for 24 hours to dry, and then poly (p-hydroxystyrene / p- (1-benzyloxyethoxy) styrene / p-acetoxystyrene ) Copolymer (resin R-5) was obtained. The weight average molecular weight was 8,400.

Synthesis Example 6

Except for using 70 g of poly (p-hydroxystyrene) (alkali-soluble resin R-1) and 22.0 g of phenethyl alcohol instead of benzyl alcohol, the same operation as in Synthesis Example 5 was carried out to give poly (p-hydroxy An oxystyrene / p- (1-phenoxyethoxy) styrene / p-acetoxystyrene) copolymer [resin R-6] was obtained. The weight average molecular weight was 13,800.

Synthesis Example 7

70 g of poly (p-hydroxystyrene / styrene) [alkaline soluble resin R-2] was dissolved in 320 g of PGMEA, and 0.35 g of p-toluenesulfonic acid pyridinium salt was further added to dissolve it at 60 ° C. The mixture was depressurized to 60 mmHg and 20 mmHg, and about 40 g of solvent was distilled off together with the water remaining in the system. It cooled to 20 degreeC, and added 8.7 g of ethyl vinyl ether. Then, stirring was continued at 20 degreeC for 5 hours. 0.3 g of triethylamine was added, 280 ml of ethyl acetate was added to the reaction mixture, and 140 ml of water and 12 ml of acetone were further added for extraction. The water washing operation was repeated three times, followed by distillation at 60 ° C. and 20 mmHg to remove water in the system, thereby obtaining a poly (p-hydroxystyrene / p- (1-ethoxyethoxy) styrene / styrene) copolymer [ Resin R-7]. The weight average molecular weight was 12600.

Synthesis Example 8

Except for using 70 g of poly (p-hydroxystyrene / tert-butylacrylate) [resin R-3], the same operation as in Synthesis Example 7 was carried out to give poly (p-hydroxystyrene / p- (1- ( Methoxyethoxy) styrene / tert-butylacrylate) copolymer [resin R-8] was obtained, and the weight average molecular weight was 22,000.

Synthesis Example 9

54.1 g of benzyl alcohol and 0.4 g of p-toluenesulfonic acid were dissolved in 230 g of PGMEA, and distilled under reduced pressure at 60 DEG C at 20 mmHg to remove water in the system. The residue was about 18 g. After cooling to 20 ° C, 50.1 g of tert-butyl vinyl ether was added and stirred for 1 hour. 0.4 g of triethylamine was added to the reaction mixture, followed by stirring. 200 ml of ethyl acetate was added thereto, followed by extraction with water with 100 ml of water. After repeating this water washing | cleaning process 3 times, ethyl acetate was distilled under reduced pressure and the mixture of acetal compounds (A-1) and (A-2) was obtained. This mixture was isolated by silica gel column chromatography.

Synthesis Example 10

Acetal compounds (A-3) to (A-8) were obtained in the same manner as in Synthesis example 9 using an alcohol compound shown in Table 1 below instead of benzyl alcohol.

(Example)

(Preparation and evaluation of radiation sensitive resin composition)

Each material shown in Table 2 was dissolved in 8 g of PGMEA, and filtered with a 0.1 µm filter to prepare a resin composition solution (resins R-7 and R-8 obtained from PGMEA solution were shown in the table in terms of solid content concentration). ).

The resin composition solution was uniformly coated on a hexamethyldisilazane-treated silicon wafer using a spin coater, and heated and dried on a heating plate at 130 ° C. for 90 seconds to form a resist film of 0.7 μm. This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) using a mask for a halftone contact hole with a transmittance of 6%, and heated on a heating plate at 110 ° C. for 90 seconds immediately after exposure. Further, the solution was developed at 23 ° C. for 60 seconds in a 2.38% aqueous tetramethylammonium hydroxide solution, rinsed with distilled water for 30 seconds, and dried.

Here, the obtained pattern was observed with the scanning electron microscope, and the performance of the following resist was evaluated.

The sensitivity was determined as the minimum exposure energy (minimum exposure amount) to which a contact hole of 0.23 mu m on the mask gives a pattern of 0.18 mu m. The resolution is expressed as the limit resolution that can be resolved with this minimum exposure amount. The side lobe (resistance) was determined by whether or not a recess of the surface caused by the sub peak light (side lobe light) occurred between the contact holes at the minimum exposure amount. X indicates that all the concave portions were not identified between the contact holes, that the concave portions having a depth of less than 0.1 µm were identified, and that the concave portions having a depth of 0.1 µm or more were identified.

As shown in the said Table 3, the composition of the Example which is this invention was excellent in all the sensitivity, resolution, and side lobe light tolerance. On the other hand, the composition of the comparative example showed insufficient data, in particular with respect to sidelobe light resistance.

According to the present invention, a chemically amplified positive photoresist composition having high resolution and high sensitivity and excellent in side lobe light resistance in exposure using a halftone mask is provided.

Claims (4)

The polymer (a) which decompose | dissolves with an acid and the solubility to alkaline developing solution increases, the compound (b) which generate | occur | produces an acid by irradiation of actinic light or a radiation, and following General formula (A) or general formula (B) The positive radiation sensitive resin composition containing 1 or more types of acetal compounds (c) shown by these are included. (Formula 1)

(In Formula (A) or Formula (B), R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms having a straight, branched or cyclic substituent, or a substituent having 7 to 18 carbon atoms. Aralkyl groups with or without retention). The polymer obtained according to claim 1, wherein the polymer (a) is reacted with an alkali-soluble polymer having a hydroxyl group, a vinyl ether compound represented by the following general formula (C), and an alcohol compound represented by the following general formula (D) under an acid catalyst. Positive type radiation sensitive resin composition characterized by the above-mentioned. (Formula 2)

(In Formula (C) or Formula (D), each of R ₃ or R ₄ independently has a linear, branched or cyclic C1-C12 substituent or an alkyl group, a C6-C18 substituent. Or an aralkyl group having or not having an aromatic group or a substituent having 7 to 18 carbon atoms). The positive radiation-sensitive property according to claim 1 or 2, wherein the total amount of the acetal compound (c) is 0.1 part by weight or more and less than 100 parts by weight with respect to 100 parts by weight of the solid content of the polymer (a). Resin composition. The positive radiation sensitive resin composition according to claim 1, further comprising an organic basic compound.