KR100657230B1 - Positive photoresist composition - Google Patents

Abstract

The present invention provides a positive photoresist composition having a small sensitivity change with time passing in the manufacture of a semiconductor device, an improved density dependency, and a sufficient sensitivity and resolution in forming a contact hole pattern. Provided is a positive photoresist composition with less occurrence of a positive photoresist composition, and a positive photoresist composition with improved edge roughness of the resist pattern and excellent storage stability.

The present invention consists of a positive photoresist composition combining a specific resin, a specific additive and a surfactant, a specific onium salt-based photoacid generator, or a specific solvent.

Description

Positive Photoresist Composition {POSITIVE PHOTORESIST COMPOSITION}

TECHNICAL FIELD This invention relates to the positive photoresist composition used for manufacture of a semiconductor integrated circuit element, the mask for integrated circuit manufacture, a printed wiring board, a liquid crystal panel.

BACKGROUND ART As a pattern forming method for manufacturing electronic components such as semiconductor devices, magnetic bubble memories, integrated circuits, and the like, a method of using a photoresist that is sensitive to ultraviolet rays or visible rays has been widely provided. The photoresist has a negative type in which the irradiated part is insolubilized in the developer by light irradiation and a positive type in which it is solubilized. On the contrary, the negative type has better sensitivity than the positive type, and has good sensitivity and chemical resistance with a substrate required for wet etching. Since it is also excellent, it has occupied the mainstream of photoresist until recently.

However, with high density and high integration of semiconductor devices and the like, the line width and spacing of the patterns become very small, and dry etching is used for etching the substrate, so that high resolution and God dry etching resistance are required for the photoresist. Positive photoresists now dominate most. In particular, since it is excellent in a sensitivity, the resolution, and dry etching resistance among positive photoresists, it is J.C. Alkali-developed positive photoresists based on alkali-soluble novolak resins, described in Strieter, Kodak Micro Electronics Seminar Proceedings, p. 116 (1976), have become the mainstream of the current process.

However, in recent years, in order to achieve higher density and higher integration in accordance with the multifunctional and advanced electronic devices, finer pattern is strongly demanded.

That is, since the dimension in the longitudinal direction is not so reduced as compared with the reduction in the horizontal dimension of the integrated circuit, the ratio of the height to the width of the resist pattern could not be increased. For this reason, suppressing the dimensional change of a resist pattern on a wafer having a complicated stepped structure has become more difficult as the pattern becomes finer.

In addition, various exposure methods have also caused problems due to the reduction of the minimum dimension. For example, in the exposure by light, the interference effect of the reflected light has a large effect on the dimensional accuracy due to the step difference of the substrate, while in the electron beam exposure, the fine effect of the fine resist pattern is caused by the proximity effect caused by the back scattering of the electrons. The ratio of height and width cannot be increased.

Many of these problems have been found to be solved by using multilayer resist systems. Multilayer resist systems are described in Solid State Technology, 74 (1981), but many other studies have been published.

In general, the multilayer resist method includes a three-layer resist method and a two-layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, and an inorganic intermediate layer and a resist are laminated thereon, and the resist is patterned. Then, the organic intermediate layer is dry-etched using this as a mask and the organic intermediate layer is used as a mask. The film is patterned by O ₂ RIE (reactive ion etching). Since this method is basically considered early because the conventional technique can be used, cracks and pinholes are formed in the intermediate layer because the process is very complicated, or because the three-layered physical property of organic film, inorganic film and organic film is laminated. It is a problem that it is easy to generate | occur | produce.

Compared to the three-layer resist method, the two-layer resist method uses a resist having both physical properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance, thereby suppressing the occurrence of cracks and pinholes. Moreover, it becomes three to two layers, and a process becomes simple. However, in the three-layer resist method, the conventional resist can be used as the upper layer resist, whereas the two-layer resist method has a problem of developing a resist having new oxygen plasma resistance.

From the above background, there is a demand for the development of a highly sensitive, high-resolution positive photoresist that is excellent in oxygen plasma resistance that can be used as an upper layer resist such as a two-layer resist method, in particular, an alkali developing resist that can be used without changing the current process. It was.

In addition, in the manufacture of ultra-LSI, which requires processing of an ultra-fine pattern having a line width of 1/2 micron or less, shortening the wavelength of use of an exposure apparatus used for lithography has progressed, and KrF excimer laser light and ArF excimer laser light are currently applied. It is approaching to use to examine. In such short wavelength photolithography, it is common to use a resist called a chemical amplification type. Among these, when ArF excimer laser light is used, it is not suitable to introduce a phenolic structure into the binder resin which is the main component of the resist from the viewpoint of optical transparency of the film, and tertiary esters such as t-butyl ester and 1-alkyladama. It is common to use as a binder the resin polymer which contains the structure which decomposes | dissolves with acid and produces | generates carboxylic acid, such as a tilester and THP protecting body of carboxylic acid, as an image forming site | part.

Si-containing polymers containing image-forming sites transparent to ArF excimer laser light are disclosed in, for example, Japanese Patent Application Laid-Open No. 8-160623, Japanese Patent Application Laid-Open No. 10-324748, Japanese Patent Application Laid-Open No. 11-60733, and Japanese Patent Publication JP-A 11-60734. In addition, SPIE, vol. 3678, pp. 241, chemically amplified resists using vinyl polymers containing tris (trimethylsilyl) silylethyl groups at the ends of acid-decomposable esters, are listed in SPIE, vol.3678, 214 and 562, respectively. A chemically amplified resist using a vinyl polymer containing trimethyl-bis (trimethylsilyl) disilaheptylmethylpropyl ester at its ester end is disclosed.

These resists had various improvements that should be made, including:

For example, the resolution in the processing of ultrafine patterns is excellent, but there is room for improvement in terms of sensitivity stability over time. In addition, in the preparation of the resist liquid, compatibility with the photoacid generator was deteriorated, turbidity occurred, or insoluble matters precipitated with time, resulting in problems with stability over time. There was also a problem with the density dependency. In order to include various patterns as a trend of devices in recent years, various performances are required for resists. One of them is roughness dependency. In the device, there are patterns where the lines are dense, on the contrary, a pattern having a wider space and an isolation pattern compared to the line. For this reason, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and the solution by the resist is not certain. In particular, in the resist system containing the resin, the performance difference between the isolation pattern and the dense pattern was remarkable, and improvement was required.

In addition, apart from the purpose of forming a fine line width, micronization is progressing also regarding the type of the hole, ie, the contact hole, through which the electrode metal of the semiconductor device has passed to the semiconductor surface, and a positive photoresist composition suitable for this is required. have. However, it has never been known how to design resist materials in order to form minute contact holes. It was confirmed that a resist suitable for obtaining a fine line width as described above is not suitable for contact hole use.

There is also room for improvement in the storage stability of the resist solution. For example, when the chemical amplification photoresist is stored in a liquid state, the compatibility between the resin and the photoacid generator is deteriorated, and there are still problems such as generation of particles in the liquid and deterioration of the resist performance. .

Moreover, the edge roughness (unevenness | corrugation) of the resist pattern generate | occur | produced even when the resolution power in the process of an ultrafine pattern was excellent. Here, the edge roughness means that the top and bottom edges of the line pattern of the resist fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist, so that the edges appear uneven when viewed from above. Say that.

It is an object of the present invention to provide a positive photoresist composition that is excellent in various properties required for the manufacture of semiconductor devices, using particular resins.

That is, as a first aspect of the present invention, there is provided a positive photoresist composition having a small sensitivity variation over time and excellent density-dependency.

As a second aspect of the present invention, there is provided a positive photoresist composition having sufficient sensitivity and resolution in the formation of a contact hole pattern and less generation of particles in the resist liquid.

As a third aspect of the present invention, there is provided a positive photoresist composition having improved edge roughness of a resist pattern and excellent storage stability in the manufacture of a semiconductor device.

It was confirmed that the above object of the present invention is achieved by combining a specific resin (component (A)) with specific various components. That is, this invention provides the composition of the following structures.

(1) (A) a compound which generates an acid by irradiation of actinic light or radiation,

(B) a resin having a partial structure represented by the following general formula (I), and having increased solubility in an alkaline developer by the action of an acid;

(C) an organobasic compound, and

(D) Positive photoresist composition containing at least 1 type of fluorine type surfactant and / or silicone type surfactant, and nonionic surfactant.

In formula (I), m represents the integer of 1-6. R ¹ and R ² may each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group. R ⁵ to R ⁷ each represent an alkyl group, a cyclic alkyl group, an aryl group, a trialkylsilyl group or a trialkylsilyloxy group.

(2) The positive photoresist composition according to the above (1), wherein the resin (A) in which the solubility in an alkaline developer is increased by the action of an acid contains a repeating unit represented by the following general formula (II).

In formula (II), R <^1> -R <^7> and m are as defined in formula (I). Y ¹ represents a hydrogen atom, a methyl group, a cyano group or a chlorine atom. L ¹ represents a single bond or a divalent linking group.

(3) The positive photoresist composition according to the above (1), wherein the resin (A) in which the solubility in an alkaline developer is increased by the action of an acid contains a repeating unit represented by the following general formula (III).

In formula (III), R <^1> -R <^7> and m are as defined in formula (I). M ¹ represents an atomic group for forming an alicyclic structure which may have a substituent together with two carbon atoms bonded thereto. n represents 1 or 2. L ² represents a single bond or an n + monovalent linking group, one side of which is connected to a carbon atom forming a ring.

(4) A sulfonium salt compound which generates an acid by irradiation with actinic light or radiation represented by (A) general formula (PAG4),

(B) A positive photoresist composition containing a resin having a partial structure represented by the general formula (I) and having increased solubility in an alkaline developer by the action of an acid.

In general formula (PAG4), Rs1-Rs3 represents the alkyl group which may respectively have a substituent, and the aryl group which may have a substituent.

In addition, two of Rs1-Rs3 may be couple | bonded through each single bond or a substituent.

Z ^- represents a counterion.

(5) The positive photoresist composition according to the above (4), wherein the sulfonium salt compound of the above-mentioned (A) is a compound represented by the following general formula [sI] and generates an acid by irradiation with actinic light or radiation.

In general formula [sI], Rs4 to Rs6 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, The acyl group which may have a substituent and the acyloxy group, nitro group, a halogen atom, a hydroxyl group, and a carboxyl group which may have a substituent are shown.

l: 1 ~ 5

m: 0-5

n: 0 to 5 are displayed.

When l + m + n = 1, Rs4 has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent The acyl group which may be used and the acyloxy group which may have a substituent are shown.

X: R-SO ₃ ,

R: The aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent are shown.

(6) (A) a compound which generates an acid by irradiation of actinic light or radiation,

(B) Resin which has the partial structure represented by said general formula (I), and whose solubility to alkaline developing solution increases by the action of an acid,

(E) containing at least one selected from the following solvent A group, at least one selected from the following solvent B group, or at least one selected from the solvent A group and at least one selected from the following solvent C group Mixed solvent

Group A: propylene glycol monoalkyl ether alkoxylate

Group B: propylene glycol monoalkyl ether, alkyl lactic acid and alkoxyalkyl propionate

Group C: Positive photoresist composition containing γ-butyrolactone, ethylene carbonate and propylene carbonate.

(7) (A) a compound which generates an acid by irradiation of actinic light or radiation,

(B) Resin which has the partial structure represented by said general formula (I), and whose solubility to alkaline developing solution increases by the action of an acid,

(E) A mixed solvent containing at least one member selected from the following solvent A group, at least one member selected from the following solvent B group, and at least one member selected from the following solvent C group

Group A: propylene glycol monoalkyl ether alkoxylate

Group B: propylene glycol monoalkyl ether, alkyl lactic acid and alkoxyalkyl propionate

Group C: Positive photoresist composition containing γ-butyrolactone, ethylene carbonate and propylene carbonate.                     

(8) (A) a compound which generates an acid by irradiation of actinic light or radiation,

(B) Resin which has the partial structure represented by said general formula (I), and whose solubility to alkaline developing solution increases by the action of an acid,

(E) Positive photoresist composition containing 1 or more types of alkyl lactate, and the mixed solvent containing 1 or more types of ester solvent and alkoxyalkyl propionate.

(9) (A) a compound which generates an acid by irradiation of actinic light or radiation,

(B) Resin which has the partial structure represented by said general formula (I), and whose solubility to alkaline developing solution increases by the action of an acid,

(E) Positive photoresist composition containing the solvent containing heptanone.

(10) The positive photoresist composition according to the above (9), wherein the (E) solvent further contains at least one of propylene glycol monoalkyl ether, alkyl lactate, and alkoxyalkyl propionate.

(11) The positive photoresist composition according to any one of (8) to (10), wherein the (E) solvent further contains one or more of γ-butyrolactone, ethylene carbonate, and propylene carbonate.

Hereinafter, the compound used for this invention is demonstrated in detail.

[1] compounds generating acid by irradiation with actinic light or radiation (component (A))

Examples of compounds (photoacid generators) that decompose upon irradiation of actinic rays or radiation used in the present invention (acid generators) include photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or micro By known light used in resists or the like (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g rays, h rays, i rays, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam The acid generating compound and mixtures thereof can be appropriately selected and used.

Moreover, as a compound which generate | occur | produces an acid by irradiation of actinic light or a radiation used for the other this invention, SI Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), TS Bal et al., Polymer , 21, 423 (1980), etc., diazonium salts, US Pat. Nos. 4,069,055, 4,069,056, and Re27,992, Japanese Patent Laid-Open No. 3- Ammonium salts described in US 140140 et al., DC Necker et al., Macromolecules , 17, 2468 (1984), CS Wen et al., Teh, Proc. Conf. Rad. Phosphonium salts described in Curing ASIA , p. 478, Tokyo, Oct. (1988), US Pat. Nos. 4, 069, 055 and 4,069,056, JV Crivello et al., Macromolecules , 10 (6) 1307 (1977) , Chem. & Eng. News , Nov. 28, p. 31 (1988), European Patent Nos. 104,143, 339,049, 410,201, iodine salts described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, JV Crivello et al., Polymer J. , 17, 73 (1985), JV Crivello et al., J. Org. Chem. , 43, 3055 (1978), WR Watt et al., J. Polymer Sci., Polymer Chem. Ed. , 22, 1789 (1984), JV Crivello et al., Polymer Bull. , 14, 279 (1985), JV Crivello et al., Macromolecules , 14 (5), 1141 (1981), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 2877 (1979), European Patents 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, 297,442, U.S. Patent 3,902,114, 4,933,377, 4,760,013 4,734,444 and 2,833,827, German Patents 2,904,626, 3,604,580, and 3,604,581, Japanese Patent Application Laid-Open Nos. 7-28237, 8-27102, etc., sulfonium salts, JV Crivello et al., Macromolecules , 10 (6), 1307 (1977), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 1047 (1979) et al., CS Wen et al., Teh, Proc. Conf. Rad. Curing ASIA , p. 478, Tokyo, Oct. Onium salts such as arsonium salts described in (1988) and the like; U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60-239736, Japanese Patent Publication No. 61-169835 Organic halogen compounds described in JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and the like; K. Meier et al., J. Rad. Curing , 13 (4), 26 (1986), TP Gill et al., Inorg. Chem. , 19, 3007 (1980), D. Astruc, Acc, Chem. Res. Organometallic / organic halogen compounds described in JP, 19 (12), 377 (1896), Japanese Patent Laid-Open No. 2-161445 and the like; S. Hayase et al., J. Polymer Sci. , 25, 753 (1987), E. Reichmanis et al., J. Polymer Sci., Polymer Chem. Ed. , 23, 1 (1985), QQ Zhu et al., J. Photochem. , 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett. , (24) 2205 (1973), DH R Barton et al., J. Chem. Soc. , 3571 (1965), PM Collins et al J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), JW Walker et al., J. Am. Chem. Soc. , 110, 7170 (1988), SC Busman et al., J. Imaging Technol. , 11 (4), 191 (1985), HM Houlihan et al., Macromolecules , 21, 2001 (1988), PM Collins et al., J. Chem. Soc. , Chem. Commun. , 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichman et al., J. Eletrochem. Soc., Solid State Sci. Technol. , 130 (6), FM Houlihan et al., Macromolecules , 21, 2001 (1988), European Patent Nos. 0,290,750, 046,083, 156,535, 271,851, and 0,388,343, US Patent 3,901,710 and Photoacid generators having o-nitrobenzyl-type protecting groups described in Japanese Patent Application Laid-Open No. 4,181,531, Japanese Patent Application Laid-Open No. 60-198538, Japanese Patent Application Laid-Open No. 53-133022, and the like; M. TUNOOKA et al., Polymer Preprints Japan , 35 (8), G. Berner et al., J. Rad. Curing , 13 (4), WJ Mijs et al., Coating Technol. , 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan , 37 (3), European Patent Nos. 0,199,672, 84,515, 044,115, 618,564 and 0,101,122 Photolysed by iminosulfonate or the like described in US Patent Nos. 4,371,605 and 4,431,774, Japanese Patent Publication No. 64-18143, Japanese Patent Application Laid-Open No. 2-245756, Japanese Patent Application Laid-Open No. 3-140109, and the like. Compounds for generating sulfonic acid, disulfone compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application Laid-Open No. 2-71270, Japanese Patent Application Laid-Open No. 3-103854, 3-103856, 4-210960, and the like. The diazoketo sulfone and the diazo disulfone compound described are mentioned.

In addition, groups which generate an acid by these light, or compounds in which the compound is introduced into the main chain or the side chain of the polymer, for example, ME Woodhouse et al., J. Am. Chem. Soc. , 104, 5586 (1982), SP Pappas et al., J. Imaging Sci. , 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., Rapid Commun. , 9, 625 (1988), Y. Yamada et al., Makromol. Chem. , 152, 153, 163 (1972), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 3845 (1979), US Patent No. 3,849,137, German Patent No. 3,914,407, Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Publication The compounds described in Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Laid-Open No. 63-163452, Japanese Patent Laid-Open No. 62-153853, Japanese Patent Laid-Open No. 63-146029 and the like can be used.

In addition, VNR Pillai, Synthesis , (1), 1 (1980), A. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), DHR Barton et al., J. Chem. Soc. (C), 329 (1970), US Patent No. 3,779,778, European Patent No. 126,712 and the like can also be used a compound which generates an acid by light.

Among the compounds that decompose upon irradiation with actinic light or radiation to generate an acid, those used particularly effectively will be described below.

(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl 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 sulfonium salt represented by general formula (PAG4).

Here, formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxy, mercapto and halogen atoms.

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

Z ^- is an anion pairs shown, and for example, _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - alkanoic acid anions, such as perfluoro- And condensed polynuclear aromatic sulfonic acid anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes such as pentafluorobenzene sulfonic acid anion, naphthalene-1-sulfonic acid anion, and the like, but are 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 specifically, there is no limitation to such a thing.

(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, an aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

Specific examples include compounds shown below, but are not limited only to these examples.

(4) diazodisulfone derivative compounds

As a diazosulfone derivative compound, what is represented by the following general formula (PAG7) is mentioned.

Here, R ²¹¹ and R ²¹² each represent an alkyl group which may have a substituent, a cycloalkyl group or an aryl group which may have a substituent.

As an alkyl group, a C1-C20 linear or branched alkyl group is preferable, More preferably, a C1-C12 linear or branched alkyl group is preferable. As a cycloalkyl group, a cyclopentyl group or a cyclohexyl group is preferable. As an aryl group, the aryl group which may have a C6-C10 substituent is preferable.

Here, as a substituent, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, Alkyl groups such as n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, halogen atom, nitro group, acetyl group, etc. have.

The following compound is mentioned as a specific example of a diazo disulfone derivative compound.

Bis (methylsulfonyl) diazomethane, bis (ethylsulfonyl) diazomethane, bis (propylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (butylsulfonyl) dia Crude methane, bis (1-methylbutylsulfonyl) diazomethane, bis (heptylsulfonyl) diazomethane, bis (octylsulfonyl) diazomethane, bis (nonylsulfonyl) diazomethane, bis (decylsul Ponyyl) diazomethane, bis (dodecylsulfonyl) diazomethane, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (benzylsulfonyl) diazomethane, Bis (2-chlorobenzylsulfonyl) diazomethane, bis (4-chlorobenzylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, Bis (2-methylphenylsulfonyl) diazomethane, bis (3-methylphenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazom , Bis (2,5-dimethylphenylsulfonyl) diazomethane, bis (3,4-dimethylphenylsulfonyl) diazomethane, bis (2,4,6-trimethylphenylsulfonyl) diazomethane, bis ( 4-fluorophenylsulfonyl) diazomethane, bis (2,4-difluorophenylsulfonyl) diazomethane, bis (2,4,6-trifluorophenylsulfonyl) diazomethane, bis ( 4-nitrophenylsulfonyl) diazomethane.

(5) diazoketosulfone derivative compounds

As a diazo keto sulfone derivative compound, what is represented by the following general formula (PAG8) is mentioned.

Here, R ^211, R ²¹² has the same meaning as R ^211, R ²¹² of the (PAG7).
As a specific example of a diazo keto sulfone derivative compound, the following compound is mentioned.

Methylsulfonyl-benzoyl-diazomethane, ethylsulfonyl-benzoyl-diazomethane, methylsulfonyl-4-bromobenzoyl-diazomethane, ethylsulfonyl-4-bromobenzoyl-diazomethane, phenylsul Phenyl-benzoyl-diazomethane, phenylsulfonyl-2-methylphenyl-diazomethane, phenylsulfonyl-3-methylphenyl-diazomethane, phenylsulfonyl-4-methylphenyl-diazomethane, phenylsulfonyl-3- Methoxyphenyl-diazomethane, phenylsulfonyl-4-methoxyphenyl-diazomethane, phenylsulfonyl-3-chlorobenzoyl-diazomethane, phenylsulfonyl-4-chlorophenyl-diazomethane, tolylsul Ponyl-3-chlorobenzoyl-diazomethane, tolylsulfonyl-4-chlorophenyl-diazomethane, phenylsulfonyl-4-fluorophenyl-diazomethane, trisulfonyl-4-fluorophenyl-diazo methane.

The amount of the compound which is decomposed by irradiation with actinic light or radiation to generate an acid is used in the range of 0.001 to 40% by weight based on the total weight of the resist composition (excluding the coating solvent), preferably 0.01 to 20 weight%, More preferably, it is used in the range of 0.1-10 weight%. If the amount of the compound decomposed 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 excessively large, resulting in deterioration of the profile. Na process (especially baking) margins become narrow and undesirable.

In addition, it was found that the contact hole resolution and the storage properties were improved by using a specific acid generator together with the resin of the component (B).

The said specific photo-acid generator is a sulfonium salt compound which generate | occur | produces an acid by irradiation of actinic light or radiation represented by the following general formula (PAG4).

In general formula (PAG4), Rs1-Rs3 represents the alkyl group which may respectively have a substituent, and the aryl group which may have a substituent.

In addition, two of Rs1-Rs3 may couple through each single bond or a substituent.

Z ^- represents a counterion.

Here, the acid generated includes sulfonic acid, carboxylic acid, disulfonylimide, N-sulfonylimide, and the like.

Here, in general formula (PAG4), Rs1-Rs3 represents the alkyl group which may respectively have a substituent, and the aryl group which may have a substituent.

Preferably, they are a C6-C14 aryl group, a C1-C8 alkyl group, and such substituted derivatives. Preferred is an aryl group. The aryl groups are phenyl group, naphthyl group, anthracene group and phenanthrene group, and the alkyl group is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, There are a heptyl group and an octyl group. Examples of these preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, nitro groups, carboxyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, hydroxy groups, mercapto groups, and halogen atoms.

Z ^- is an anion pairs shown, and for example, _{^{BF 4 -, AsF 6 -,}} PF 6 -, SbF 6 -, SiF 6 2-, ClO 4 -, CF 3 SO 3 - alkanoic acid anions, such as perfluoro- And sulfonic acid anions having an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as pentafluorobenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dye, and alkylsulfonic acid such as methanesulfonic acid. It is not limited to this.

In addition, two of Rs1-Rs3 may be couple | bonded through each single bond or a substituent.

Specific examples of the photoacid generator represented by General Formula (PAG4) include the following (PAG4-1) to (4-37).

Moreover, the photo-acid generator represented by the said general formula [sI] is especially preferable. Thereby, the number of particles after liquid-forming a resist composition solution and the number of increase of the particle | grains after time storage by the liquid preparation can be further reduced.

As the alkyl group of Rs4 to Rs6 in the general formula [sI], a methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, which may have a substituent There exists a C1-C25 thing, such as a hexyl group, a heptyl group, an octyl group, t-amyl group, a decanyl group, a dodecanyl group, and a hexadecanyl group. The cycloalkyl group may have 3 to 25 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecanyl group, a cyclohexadecanyl group and the like which may have a substituent. As the alkoxy group, a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group, pentyloxy group and t-amyl may have a substituent. There exists a C1-C25 thing, such as an oxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group.

As the alkoxycarbonyl group, a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group or t-butoxycarbonyl group and pentyl may have a substituent. There exists a C2-C25 thing, such as an oxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group, etc. Examples of the acyl group include those having 1 to 25 carbon atoms such as formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group and t-amylcarbonyl group which may have a substituent. As an acyloxy group, the acetoxy group which may have a substituent, an ethyloxy group, butyryloxy group, t-butyryloxy group, t-amiryloxy group, n-hexane carbonyloxy group, n-octane carbonyloxy group, There exists a C2-C25 thing, such as an n-dodecane carbonyloxy group and n-hexanedecane carbonyloxy group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom or iodine atom.

Preferred substituents for the group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, nitro And the like can be mentioned.

In addition, when l + m + n = 1, Rs4 is an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent The acyl group which may have a substituent and the acyloxy group which may have a substituent is shown. In this case, Rs4 is preferably 2 or more carbon atoms, more preferably 4 or more carbon atoms.

Among the above, alkyl groups which may have substituents of Rs4 to Rs6 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, n-pentyl, t-amyl and n-hex. A carboxyl group, a n-octyl group, and a decanyl group are preferable, and a cyclohexyl group which may have a substituent as a cycloalkyl group, a cyclooctyl group, and a cyclododecanyl group is preferable, and an alkoxy group may have a substituent as a methoxy group. , Ethoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecane An oxy group is preferable, and as the alkoxycarbonyl group, a methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbon A carbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group are preferable, and the acyl group may have a substituent, a formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group , t-amylcarbonyl group is preferable, and the acyloxy group may be an acetoxy group, an ethyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amiryloxy group, or an n-hexanecarbonyloxy group which may have a substituent. and n-octanecarbonyloxy group are preferable.

Among the above substituents, specific examples of more preferable Rs4 to Rs6 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t-amyl group and n-hexyl group , n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group , Methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, butyryl group, hexanoyl group, octanoyl group Noyl group, t-butylcarbonyl group, t-amylcarbonyl group, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy group, t-amiryloxy group, n-hexanecarbonyloxy group, n-octanecarbonyl jade It is a period, a hydroxyl group, a chlorine atom, a bromine atom, and a nitro group.

As the substituent for the group, a methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group and t-amyloxycarbonyl group are preferable. .

The sulfonium compound represented by the general formula [sI] used in the present invention uses sulfonic acid having the specific structure as described above with X ⁻ as its counterion.

Examples of the aliphatic hydrocarbon group which may have a substituent of R in the counterion include a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group. In addition, the aromatic group which R may have a substituent is mentioned.

The alkyl group of R may be a methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group or dodecyl group which may have a substituent. C1-C20, such as these, is mentioned. Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, tricyclodecanyl group, menthyl group etc. which may have a substituent are mentioned as cyclic alkyl group. As an aromatic group, the phenyl group, naphthyl group, etc. which may have a substituent are mentioned.

Among the above, alkyl groups which may have a substituent of R include methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, n-propyl and n-butyl. , Nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, cyclopentyl group, cyclo Hexyl group and camphor group are mentioned. As the aromatic group, a phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group, p-hydroxyphenyl group, p-methoxyphenyl group and dodecylphenyl group which may have a substituent , Mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.

Specific examples of the more preferable sulfonic acid substituent R include methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-butyl group, nonafluorobutyl group, n-hexyl group , n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group, p- Methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.

As total carbon number of the generated acid, 1-30 pieces are preferable. More preferably, it is 1-28 pieces, More preferably, it is 1-25 pieces. If the total number of carbon atoms is less than one, the formation of the t-top shape may be hindered, and if the total number of carbon atoms is more than 30, the development residue may occur.

Although the following [sI-1]-[sI-20] are shown by the specific example of a compound represented by general formula [sI] below, this invention is not limited to this. These compounds are used individually or in combination of 2 or more types.

The compound (photoacid generator) which generate | occur | produces an acid by irradiation of actinic light or radiation represented by the said general formula [sI] may use together the other photo-acid generator mentioned above.

The onium salt represented by (PAG4) or [sI] is the same as the onium salt represented by the general formulas (PAG3) and (PAG4), which is described, for example, in JW Knapczyk et al., J. Am. Chem. Soc. , 91, 145 (1969), AL Maycok et al., J. Org. Chem. , 35, 2532 (1970), E. Goethas et al., Bull. Soc. Chem. Belg. , 73, 546 (1964), HM Leicester, J. Ame. Chem. Soc. 51, 3587 (1929), JV Crivello et al., J. Polym. Chem. Ed. , 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Publication No. 53-101331 and the like.

The amount of the compound that is decomposed by irradiation with actinic rays or radiation represented by the general formula (PAG4) or [sI] to generate an acid is generally based on the total weight of the resist composition (excluding the coating solvent). It is used in the range of 0.01-20 weight%, Preferably it is 0.1-15 weight%, More preferably, it is used in the range of 0.5-10 weight%. If the amount of the compound decomposed by irradiation with actinic rays or radiation to generate an acid is less than 0.01% by weight, the sensitivity is lowered. If the amount is more than 20% by weight, the light absorption of the resist is too high, resulting in deterioration of the profile or process. The margin is narrowed (especially baking), which is undesirable. In addition, the photoacid generator which can be used together is 300 weight% or less of the addition amount of the acid generator of this invention, Preferably it is 200 weight% or less, More preferably, it is 100 weight% or less.

[2] Next, a resin (also referred to as an acid-decomposable polymer or an acid-decomposable resin) in which the solubility in an alkaline developer is increased by the action of an acid as (B) component is described.

Acid-decomposable resin (B) of the present invention is characterized by having a partial structure represented by the general formula (I).

In said general formula (I), as an alkyl group which R <^1> -R <^4> represents, a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, Furthermore, Preferred are methyl group, ethyl group, n-butyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group, and these alkyl groups may have a substituent.

Examples of the cyclic alkyl group represented by R ¹ to R ⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, which may have a substituent. Isobornyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and the like.

Examples of the alkyl group and the cyclic alkyl group for R ⁵ to R ⁷ include the same as those described above for R ¹ to R ⁴ . An aryl group may have a substituent, and a phenyl group, a tolyl group, a naphthyl group, etc. are specifically, mentioned. As an alkyl group of a tolylalkyl silyl group, a C1-C6 linear or branched alkyl group is preferable, More preferably, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s -Butyl group and t-butyl group, and most preferable among these is a methyl group. As an alkyl group of a trialkylsilyloxy group, a C1-C6 linear or branched alkyl group is preferable, More preferably, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, S-butyl group and t-butyl group are the most preferable among these, a methyl group.

Although the specific example of the structural unit represented by general formula (I) is shown below, this invention is not limited to this.

The acid-decomposable resin (B) having a partial structure represented by the general formula (I) of the present invention preferably contains a repeating unit represented by the general formula (II) or a repeating unit represented by the general formula (III). .                     

In general formula (II), as a bivalent coupling group in L <^1> , a cycloalkylene group, ether group, thioether group, carbonyl group, ester group, amide which may have a single bond, an alkylene group, a substituted alkylene group, and a crosslinked structure The group selected from the group consisting of a group, a sulfonamide group, a urethane group, and a urea group or a combination of two or more groups can be mentioned.

Examples of the alkylene group and substituted alkylene group for L ¹ include groups represented by the following formulas.

[C (Rα) (Rβ)] _r −

In the formula, Rα and Rβ represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group and an alkoxy group, and the two may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably is selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r represents the integer of 1-10.

Examples of the cycloalkylene group which may have a crosslinked structure include those having 5 to 8 carbon atoms, and specific examples include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a norbornylene group.

Although the following are mentioned as a specific example of the repeating unit represented by the said General formula (II), This invention is not limited to this.

In the above general formula (III), the atomic group for forming M ¹ in the alicyclic structure is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and among these, a monocyclic 5- to 8-membered ring Or an atomic group for forming a pedestrian alicyclic structure that forms a repeating unit of a cyclic alicyclic hydrocarbon.

Examples of the skeleton of the aliphatic alicyclic hydrocarbon include those represented by the following structures.

The skeleton of the alicyclic hydrocarbon may have a substituent. Such substituents include halogen atoms, cyano groups, -COOH, -COOR ¹⁰ (wherein R ¹⁰ represents an alkyl group, a cyclic hydrocarbon group, or a group decomposed by the action of an acid), -CO-XTR, or a substituent There may be a good alkyl group or cyclic hydrocarbon group. Wherein X represents an oxygen atom, a sulfur atom, -NH- or -NHSO _2- , T represents a single bond or a divalent linking group, R ¹⁰ represents a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ¹¹ , -CO-NH-R ¹² , an alkyl group which may be substituted, an alkoxy group which may be substituted, or a cyclic hydrocarbon group which may be substituted (may have an ester group or a carbonyl group in the bond to form a ring). R ¹¹ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent (may have an ester group or a carbonyl group in the bond to form a ring), and R ¹² represents an alkyl group which may have a substituent Is displayed.

The divalent linking group in L ^{2 may be selected} from the group consisting of alkylene group, substituted alkylene group, ether group, thioether group, carbonyl group, ester group, amide group, sulfonamide group, urethane group and urea group. There is a combination of the above groups.

Examples of the alkylene group and substituted alkylene group for L ² include the same as the divalent linking group for L ¹ in General Formula (II).

Although the following are mentioned as a specific example of the repeating unit represented by the said General formula (III), This invention is not limited to this.

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It is preferable that the resin of this invention further contains the repeating unit represented with the following general formula (IV) further. This improves the roughness dependency.

In formula (IV), Z represents an oxygen atom or = NR ¹³ . R ¹³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ¹⁴ . R ¹⁴ represents an alkyl group or a trihalomethyl group.

In general formula (IV), as an alkyl group of R <^13> , R <^14> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group And an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group.

Although the following are mentioned as a specific example of the repeating unit represented by said general formula (IV), This invention is not limited to this specific example.

In addition, the resin of the present invention may contain a repeating unit represented by the following General Formula (V).

In formula (V), Y <^2> represents a hydrogen atom, a methyl group, a cyano group, or a chlorine atom. L ³ represents a single bond or a divalent linking group. Q represents a group which can be decomposed by a hydrogen atom or an acid to generate a carboxylic acid.

In the repeating unit (V), a group that can be decomposed by an acid to generate carboxylic acid is a group that decomposes / decomposes in a resin to generate a -COOH group by an acid generated in the component (A) by exposure. Specifically, such groups include tertiary alkyl groups such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyl Alkoxymethyl groups, such as 1-alkoxyethyl group, 1-methoxymethyl group, and 1-ethoxymethyl group, such as an oxyethyl group, tetrahydropyranyl group, tetrahydrofurfuryl group, a trialkylsilyl group, 3-oxocyclohexyl group, 2- Methyl adamantyl group, mevalonic lactone residue, 2-((gamma) -butyrolactyl ylcarbonyl) -2-propyl group, etc. are mentioned.

Specific examples of the repeating unit represented by General Formula (V) include the following, but the present invention is not limited to these specific examples.

The resin of the present invention may further contain other repeating units in addition to the above repeating units.

As such another repeating unit, a repeating unit represented by the following general formula (VI) is preferable.

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In formula (VI), R ¹⁵ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted straight or branched alkyl group having 1 to 4 carbon atoms. Several R <^15> may be same or different, respectively. B represents a halogen atom, a cyano group, a group decomposed by the action of an acid, -C (= O) -WUR ¹⁶ or -COOR ¹⁷ .

Here, W represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-, R ¹⁶ is -COOH, -COOR ¹⁸ (R ¹⁸ is the same meaning as R ¹⁷ , the following lactone shows the structure), -CN, a hydroxyl group, which may have a substituent represents a alkoxy ^{group, -CO-NH-R 17,} -CO-NH-SO 2 -R 17 or a lactone structure.

In the lactone structure, Ra to Re each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent. m and n respectively independently represent the integer of 0-3, and m + n is 2 or more and 6 or less.

R ¹⁷ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent, U represents a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, The sole or combination of two or more groups selected from the group consisting of sulfonamide groups, urethane groups and urea groups is indicated.

The group decomposed by the action of the acid is preferably a group represented by -C (= O) -X ¹ -R ⁰ . Here, as R ⁰ , tertiary alkyl groups such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group And alkoxymethyl groups such as 1-alkoxyethyl groups, 1-methoxymethyl groups, and 1-ethoxymethyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, trialkylsilyl groups, and 3-oxocyclohexyl groups. X ¹ represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-, but an oxygen atom is preferable.

As said alkyl group, a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

As said cyclic hydrocarbon group, it is a cyclic alkyl group and a piercing hydrocarbon group, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a boronyl group, an isoboroyl group, a tricyclo decanyl group, a dicyclopente A nil group, a norbornane epoxy group, a menthyl group, an isomentyl group, a neomentyl group, the tetracyclo dodecanyl group, etc. are mentioned.

Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Examples of other substituents in the alkyl group, cyclic alkyl group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, acyl group include formyl group and acetyl group, and acyloxy group include acetoxy group and the like. Can be mentioned.

Examples of the alkylene group and substituted alkylene group of A in Formula (VI) include the groups shown below.

[C (Rγ) (Rδ)] _s-

Wherein Rγ and Rδ represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and the two may be the same or different, and an alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or the like. Lower alkyl groups are preferred, and more preferably, a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group is represented. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. s represents the integer of 1-10.

In the above, the halogen atom includes chlorine atom, bromine atom, fluorine atom and iodine atom.

The B roneun preferred is represented by the acid-decomposable group, -COOR ¹⁶ (lactone structure).

Moreover, it is preferable that the acid-decomposable resin in this invention contains the repeating structural unit represented by the following general formula (VII) and / or (VIII). By this, problems due to the hydrophobicity of the resist composition can be improved.

In said Formula (VII)-(VIII), R <^20> is synonymous with R <^15> of the said General formula (VI). R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group which may have a substituent.

L ⁴ represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group having a combination thereof.

V represents either of the functional groups shown below.

In general formula (VII) and (VIII), the alkyl group of R <^21> , R <^22> may be linear, branched, or may have a substituent. As a linear or branched alkyl group, it is preferable that it is C1-C12, More preferably, it is C1-C10, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group , sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group are preferable.

Although cyclic alkyl groups of R ²² have 3 to 30 carbon atoms, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group And nobornane epoxy group, menthyl group, isomentyl group, neomentyl group, detracyclodecanyl group, steroid residue, etc. are mentioned.

Examples of the aryl group for R ²² include one having 6 to 20 carbon atoms, and may have a substituent. Specifically, a phenyl group, tolyl group, a naphthyl group, etc. are mentioned.

Examples of the aralkyl group for R ²² include one having 7 to 20 carbon atoms, and may have a substituent. Specifically, a benzyl group, a phenethyl group, a cumyl group, etc. are mentioned.

L ⁴ represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group combining these.

R <^21> represents a single bond, an alkylene group, an arylene group, or the bivalent group which combined these.

In R <^21> , although the arylene group has C6-C10, you may have a substituent. Specifically, a phenylene group, tolylene group, naphthylene group, etc. are mentioned.

The alkylene group in L ⁴ , R ²¹ has the same meaning as that of V in General Formula (VI).

As the other substituent in the alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group, arylene group, carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, There are an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group.

Examples of the alkyl group include lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropyl group, cyclobutyl group and cyclopentyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. As acyloxy group, an acetoxy group etc. are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom.

In general formula (VIII), R ²¹ is preferably an alkylene group such as a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, and R ²² is an alkyl group having 1 to 10 carbon atoms, such as a methyl group or an ethyl group, or a cyclopropyl group. Cyclic alkyl groups, such as a cyclohexyl group and a camphorzan group, a naphthyl group, and a naphthyl group methyl group are preferable. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond.

Hereinafter, although the specific example of the monomer corresponding to the repeating structural unit represented by general formula (VIII) is shown, it is not limited to this.                     

The acid-decomposable resin of the present invention has various repeating structures for the purpose of controlling dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are generally required characteristics of the resist, in addition to the repeating structural unit. It may contain units.

Although the repeating structural unit corresponding to the following monomer is mentioned as such a repeating structural unit, It is not limited to this.

Thereby, the performance required for an acid-decomposable resin, especially

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(1) solubility in coating solvents,

(2) film forming property (glass transition point),

(3) alkali developability,

(4) membrane loss (select hydrophilic, alkali-soluble group),

(5) adhesion to the unexposed portion of the substrate,

(6) dry etching resistance

Fine adjustment of the back and the like becomes possible.

As such a monomer, for example, one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. The compound etc. which are held are mentioned.

Specifically, the following monomers are mentioned.

Acrylic esters (preferably alkyl acrylate having 1 to 10 carbon atoms in the alkyl group):

Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl Acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylic acid esters (preferably alkyl methacrylate having 1 to 10 carbon atoms in the alkyl group):

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monometha Methacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides:

Acrylamide, N-alkylacrylamide, (The alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxy Ethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.) , N-hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide and the like.

Methacrylamides:

Methacrylamide, N-alkyl methacrylamide (as alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N , N-dialkyl methacrylamide (the alkyl group includes ethyl group, propyl group, butyl group and the like), N-hydroxyethyl-N-methylmethacrylamide and the like.

Allyl Compounds:

Allyl esters (for example, allyl acetate, allyl capronate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearic acid, allyl benzoate, allyl benzoate, allyl lactate, and the like), allyloxyethanol and the like.

Vinyl ethers:

Alkyl vinyl ether (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofur Furyl vinyl ether and the like.

Vinyl esters:

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl aceto acetate, vinyl lactate, Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Itaconic acid alkyls:

Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.

Dialkyl esters or monoalkyl esters of fumaric acid; Dibutyl fumarate and the like.
Others include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleylonitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the said various repeating structural units, it may be copolymerized.

In acid-decomposable resins, the molar ratio of each repeating structural unit is suitably used to control dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and the like, which are generally required performance of resist. Can be set.

In the resin according to the present invention, the content of the repeating unit containing the partial structure represented by the general formula (I) of the present invention is O ₂ plasma etching resistance, sensitivity, pattern cracking prevention, substrate adhesion, resist profile, Or it can set suitably in consideration of the resolution, heat resistance, etc. which are a requirement of a general resist. In general, the content of the repeating unit (preferably the repeating unit represented by the general formula (II) and / or the general formula (III)) having a partial structure represented by the general formula (I) of the present invention is the total monomer of the resin. 4-70 mol% of a repeating unit is suitable, Preferably it is 6-65 mol%, More preferably, it is 8-60 mol%.

Moreover, although content in resin of the repeating unit represented by said general formula (IV)-(VIII) can also be set suitably according to the performance of a desired resist, generally 30-96 mol% is suitable, Preferably it is 35- 94 mol%, Especially preferably, it is 40-92 mol%. Moreover, when it contains another repeating unit other than 50 mol%, Preferably it is 40 mol% or less, More preferably, it is 30 mol% or less of all the repeating units.

The resin of the present invention is synthesized by copolymerizing the monomer of the copolymer component in the presence of a polymerization catalyst when using a copolymer component different from the monomer corresponding to the repeating unit represented by the general formula (II) and / or general formula (III). can do.

The weight average molecular weight of resin which concerns on this invention is preferably 1,000-200,000 as polystyrene conversion value by GPC method. If the weight average molecular weight is less than 1,000, deterioration of heat resistance and dry etching resistance is observed, which is not preferable. If the weight average molecular weight is more than 200,000, developability is deteriorated or the viscosity becomes very high. do.

Although the specific example of the acid-decomposable resin of this invention is listed below, this invention is not limited to this.

In the positive photoresist composition of the present invention, the blending amount in the whole composition of the resin (polymer) according to the present invention is preferably 40 to 99.99% by weight, more preferably 50 to 99.97% by weight of the total resist solids.

[3] An organic basic compound as the component (C) for the positive photoresist composition of the present invention will be described. Some of these organobasic compounds have the following structures.

Where R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl having 6 to 20 carbon atoms. And R ²⁵¹ and R ²⁵² may combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

More preferred compounds are nitrogen-containing basic compounds having at least two nitrogen atoms of different chemical environments in one molecule, particularly preferably compounds containing both substituted and unsubstituted amino groups and ring structures containing nitrogen atoms or alkylamino groups It is a compound having. Preferred detailed examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or substituted 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 pipepe Razine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferable 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.

Specific preferred compounds include 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-diaminopyri Midine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpho Lean, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0] undeca- 7-ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea Tertiary morpholine derivatives, such as (CHMETU), the hindered amines (for example, those described in the said publication), etc. of Unexamined-Japanese-Patent No. 11-52575, etc. are mentioned, It is limited to these. no.

Particularly preferred embodiments are 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-diazabicyclo [5,4,0] undeca-7-ene, 1,4- Diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, Tertiary morpholines, such as CHMETU, Hindered amines, such as bis (1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, etc. are mentioned.

Among them, 1,5-diazabicyclo [4,3,0] nona-5-ene and 1,8-diazabicyclo [5. 4.0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate is preferred.

These organic basic compounds are used individually or in combination of 2 or more types. The amount of the organic basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight based on the total solids of the resist composition. If it is less than 0.001 weight%, the addition effect of the said organic basic compound is not acquired. On the other hand, when it exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

[4] A surfactant as the component (D) for the positive photoresist composition of the present invention will be described. (D) component is a fluorine-type surfactant, a silicone type surfactant, surfactant containing both a fluorine atom and a silicon atom, and 1 or more types of surfactant of nonionic surfactant. Among these, fluorine-based surfactants, silicone-based surfactants, and surfactants containing both fluorine and silicon atoms are particularly preferable, and the density dependency can be improved.

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As these surfactants, for example, Japanese Patent Publication No. 62-36663, Japanese Patent Publication No. 61-226746, Japanese Patent Publication No. 61-226745, Japanese Patent Publication No. 62-170950, Japanese Patent Publication No. 63 -34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988, United States Patent 5405720, East 5360692, East Surfactant as described in 5529881, 5296330, 5436098, 5576143, 5294511, 5824451 is mentioned, The following commercially available surfactant can also be used as it is.

Commercially available surfactants that can be used include, for example, Eftop EF301 and EF303 (manufactured by Shin Akita Kasei Co., Ltd.), Florad FC430 and 431 (manufactured by Sumitomo 3M Corporation), Megafac F171, F173, F176, F189 and R08 ( Fluorine-based compounds such as Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (Asahi Glass Co., Ltd.), Troisol S-336 (Troy Chemical Co., Ltd.) Surfactant or silicone type surfactant can be mentioned. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) may also be used as the silicone-based surfactant.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether. Polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monool Sorbitan fatty acid esters such as latex, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxy Ethylene Sorbitan Trioleate, Polyoxyethylene And nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate.

The compounding quantity of surfactant is 0.01 weight%-2 weight% generally based on solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%.

These surfactants may be added alone or in combination of some.

[5] Next, the solvent will be described. The positive photoresist composition of the present invention is propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, lactic acid alkyl esters such as methyl lactate and ethyl lactate, and propylene glycol monomethyl as a coating solvent. Propylene glycol monoalkyl ethers such as ether and propylene glycol monoethyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like. Alkyl alkoxypropionates such as ethylene glycol monoalkyl ether acetates, 2-heptanone, γ-butyrolactone, methyl methoxy propionate and ethyl ethoxypropionate, alkyl pyruvate esters such as methyl pyruvate and ethyl pyruvate, and N- Me Is applied using a pyrrolidone, N, N- dimethylacetamide, one or more kinds of solvents selected from dimethyl sulfoxide.

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In addition, it was confirmed that by using a specific solvent or a mixed solvent ((E) component) with respect to the solvent, the edge roughness and the time-lapse stability of the resist solution were improved.

The solvent as the component (E) is one or more of propylene glycol monoalkyl ether carboxylates (called a solvent of group (A)), and one or more of propylene glycol monoalkyl ether, alkyl lactic acid and alkoxyalkyl propionate ( It is a mixed solvent containing (the group (B) solvent) and / or (gamma) -butyrolactone, ethylene carbonate, and a propylene carbonate (the solvent of group (C)). That is, as the component (E), a combination of a group A solvent and a group B solvent, a combination of a group A solvent and a group C solvent, a group A solvent, a group B solvent, and a group C solvent are used. do. When the combination of the solvent of group A and the solvent of group B is used, the edge roughness is particularly excellent. The combination of the solvent of A and the solvent of group C is particularly excellent in stability over time of the resist liquid. When a combination of a group A solvent, a group B solvent, and a group C solvent is used, both the edge roughness and the time-lapse stability of the resist liquid are excellent.

As propylene glycol monoalkyl ether carboxylate, a propylene glycol monomethyl ether acetate, a propylene glycol monomethyl ether propionate, a propylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether propionate are mentioned preferably.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether are mentioned preferably. Examples of the alkyl lactate include methyl lactate and ethyl lactate. As an alkoxy alkyl propionate, 3-ethoxy ethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, 3-ethoxymethyl propionate is mentioned preferably.

The use weight ratio (A: B) of the solvent of the group A and the solvent of the group B is preferably 90:10 to 15:85, more preferably 85:15 to 20:80, still more preferably 80: 20-25: 75.

The use weight ratio (A: C) of the solvent of group A and the solvent of group C is preferably 99.9: 0.1 to 75:25, more preferably 99: 1 to 80:20, still more preferably 97: 3-85: 15.

When combining these three solvents, the use weight ratio of the solvents of group C is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, most preferably 3 to 17, based on the total solvent. Weight percent.

As a preferable combination of the mixed solvent containing the propylene glycol monoalkyl ether carboxylate in this invention,

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid

Propylene Glycol Monomethyl Ether Acetate + 3-Ethoxyethyl Propionate

Propylene Glycol Monomethyl Ether Acetate + γ-butyrolactone

Propylene Glycol Monomethyl Ether Acetate + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Propylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + 3-Ethoxyethyl Propionate + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + 3-Ethoxyethyl Propionate + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + Propylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + Propylene Carbonate                     

Propylene glycol monomethyl ether acetate + 3-ethoxyethyl propionate + propylene carbonate.

As a particularly preferable combination of solvents,

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + 3-Ethoxyethyl Propionate + γ-Butyrolactone

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + 3-Ethoxyethyl Propionate + Ethylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Propylene Glycol Monomethyl Ether + Propylene Carbonate

Propylene Glycol Monomethyl Ether Acetate + Ethyl Lactic Acid + Propylene Carbonate

Propylene glycol monomethyl ether acetate + 3-ethoxyethyl propionate + propylene carbonate.

Moreover, as (E) component of this invention, 1 or more types (the solvent of (1)) in alkyl lactate, and 1 or more types (the solvent of (2)) in ester solvent and alkoxyalkyl propionate are mentioned. Mixed solvents to contain are also mentioned. When the combination of the solvent of (1) and the solvent of (2) is used, especially edge roughness is excellent. Preferred alkyl lactates include methyl lactate and ethyl lactate.

Preferable examples of the ester solvent include butyl acetate, pentyl acetate, hexyl acetate, butyl propionate, and the like, and more preferably butyl acetate. As an alkoxy alkyl propionate, 3-ethoxy ethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, 3-ethoxymethyl propionate is mentioned preferably.

As for the use weight ratio ((1) :( 2)) of the solvent of said (1) and the solvent of (2), 90: 10-15: 85 are preferable, More preferably, it is 85: 15-20: 80, More preferably, it is 80: 20-25: 75.

In this invention, it is preferable to further contain at least 1 type (the solvent of (3)) among (gamma) -butyrolactone, ethylene carbonate, and propylene carbonate in the said mixed solvent as (E) component. By adding the solvent of (3), generation | occurrence | production of particle | grains in a resist composition solution can be suppressed, and particle | grain generation at the time of this solution can also be suppressed.

As for the use weight ratio of the solvent of (3), 0.1-25 weight% is preferable with respect to the whole solvent, 1-20 weight% is more preferable, More preferably, it is 3-15%.

Preferred combinations of the mixed solvent containing alkyl lactate in the present invention include ethyl lactate + butyl acetate, ethyl lactate + butyl acetate + gamma -butyrolactone, ethyl lactate + butyl acetate + ethylene carbonate, ethyl lactate + butyl acetate + propylene Carbonate, ethyl lactate + 3-ethoxyethyl propionate + gamma -butyrolactone, ethyl lactate + 3-ethoxyethyl propionate + ethylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + propylene carbonate More preferably, ethyl lactate + butyl acetate + gamma -butyrolactone, ethyl lactate + butyl acetate + ethylene carbonate, ethyl lactate + butyl acetate + propylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + gamma- Butyrolactone, ethyl lactate + 3-ethoxyethyl propionate + ethylene carbonate, ethyl lactate + 3-ethoxyethyl propionate + propylene carbonate.

Moreover, the solvent containing heptanone (called the solvent of (4)) is also mentioned as (E) component of this invention. Examples of heptanone include 2-heptanone, 3-heptanone, and 4-heptanone, and 2-heptanone is preferable. By using a heptanone solvent, the edge roughness of a resist pattern becomes good. Moreover, it is preferable that (E) component further contains 1 or more types (it is called (5) solvent) among propylene glycol monoalkyl ether, alkyl lactate, and alkoxy alkyl propionate. As a result, the edge roughness of the resist pattern is further improved.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether are mentioned preferably. Examples of the alkyl lactate include methyl lactate and ethyl lactate. As an alkoxy alkyl propionate, 3-ethoxy ethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, 3-ethoxymethyl propionate is mentioned preferably.

The usage-amount of the solvent of said (4) is generally 30 weight% or more with respect to all the solvents, Preferably it is 40 weight% or more, More preferably, it is 50 weight% or more. The usage-amount of the solvent of (5) is 5 to 70 weight% generally with respect to the whole solvent, Preferably it is 10 to 60 weight%, More preferably, it is 15 to 50 weight%. When the usage-amount of the solvent of (5) is less than the said range, the addition effect will fall, and when it exceeds 70 weight%, problems, such as deterioration of applicability | paintability, may arise, and are unpreferable.

In this invention, it is preferable that the solvent of (E) further contains 1 or more types (it is called (6) solvent) of (gamma) -butyrolactone, ethylene carbonate, and propylene carbonate. By adding the solvent of (6), it can suppress generation | occurrence | production of particle | grains in the resist composition solution, and can also suppress generation | occurrence | production of particle | grains at the time of this solution.

As for the use weight ratio of the solvent of (6), 0.1-25 weight% is preferable with respect to the whole solvent, 1-20 weight% is more preferable, More preferably, it is 3-15 weight%.

Preferred combinations of the mixed solvent containing heptanone in the present invention include 2-heptanone + propylene glycol monomethyl ether, 2-heptanone + ethyl lactate, 2-heptanone + 3-ethoxyethyl propionate, 2 -Heptanone + γ-butyrolactone, 2-heptanone + ethylene carbonate, 2-heptanone + propylene carbonate, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + gamma -butyrolactone, 2-heptanone + 3-ethoxyethylpropionate + gamma -butyrolactone, 2-heptanone + propylene glycol monomethyl ether + ethylcarbonate, 2-heptanone + ethyl lactate + ethylene Carbonate, 2-heptanone + 3-ethoxyethylpropionate + ethylene carbonate, 2-heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3 Ethoxyethyl Propionate + Propylene Carbonate to be. More preferred is 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + 3-ethoxyethylpropionate + γ- Butyrolactone, 2-heptanone + propylene glycol monomethyl ether + ethylene carbonate, 2-heptanone + ethyl lactate + ethylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + ethylene carbonate, 2-heptanone + Propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + propylene carbonate.

In this invention, it is preferable to melt | dissolve 3-25 weight% of solid content of the resist composition containing each said component in the said solvent or mixed solvent at solid content concentration, More preferably, it is 5 to 22 weight%, More preferably, 7 20 wt%.

The positive photoresist composition of the present invention may further contain an acid decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant other than the above, a photosensitizer, a compound for promoting solubility in a developer, and the like.

Such a positive photoresist composition of the present invention is applied onto a substrate to form a thin film. As for the film thickness of this coating film, 50 nm-1.5 micrometers (1500 nm) are preferable.

The composition is applied onto a substrate (e.g., silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit devices by a suitable coating method such as a spinner, a coater, etc., then exposed through a predetermined mask, baked and developed. A good resist pattern can be obtained. Here, as exposure light, what is preferable is far ultraviolet of 250 nm or less, More preferably, a wavelength of 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, an electron beam, etc. are especially preferable, ArF excimer laser (193 nm) is preferable.

As a developing solution of the positive photoresist composition for far ultraviolet exposure 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, Second amines such as diethylamine and di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethyl Alkaline aqueous solutions, such as quaternary ammonium salts, such as ammonium hydroxide, cyclic amines, such as a pyrrole and a piperidine, can be used.

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

When the resist by the positive photoresist composition of the present invention is used as an upper resist of a two-layer resist, etching is performed by oxygen plasma of the lower organic polymer film using an upper resist pattern as a protective mask, but this upper resist is an oxygen plasma. Sufficient resistance to Oxygen plasma resistance of the positive photoresist composition of the present invention varies depending on the silicon content of the upper layer resist, the etching apparatus, and the etching conditions, but the etching selectivity (the etching rate ratio of the lower layer and the upper layer resist) is sufficient to be 10 to 100. Can be made larger.

In the pattern forming method using the positive photoresist composition of the present invention, an organic polymer film is first formed on the substrate to be processed. The organic polymer film may be any known photoresist, and examples thereof include FH series manufactured by FUJIFILM ORIN, FHi series, OIR series manufactured by ORIN, and PFI series manufactured by Sumitomo Kagaku Co., Ltd. . Formation of this organic polymer film is performed by dissolving this in a suitable solvent and applying the solution obtained by a spin coater method, a spray method, etc. Next, a film of the positive photoresist composition of the present invention is formed on the first layer of the organic polymer film. This is done by dissolving the resist material in a suitable solvent similarly to the first layer, and applying the obtained solution by a spin coater method, a spray method, or the like.

The obtained two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first applied to the film of the second layer, that is, the upper photoresist composition. Masking is performed as needed, and a high energy ray is irradiated through this mask, the photoresist composition of an irradiation part is soluble in aqueous alkali solution, it develops in aqueous alkali solution, and a pattern is formed.

Next, although the organic polymer film is etched as a second step, this operation is performed by oxygen plasma etching using the above-described pattern of the resist composition film as a mask to form a fine pattern having a high aspect ratio. The etching of the organic polymer film by this oxygen plasma etching is a technique exactly the same as that of the plasma ashing used in the peeling of the resist film, which is performed after the etching processing of the substrate by the conventional photoetching operation. This operation can be carried out using, for example, oxygen as a reactive gas, that is, an etching gas, by a cylindrical plasma etching apparatus or a parallel plate plasma etching apparatus.

Although the substrate is processed using this resist pattern as a mask, dry etching methods such as sputter etching, gas plasma etching, and ion beam etching can be used as the processing method.

The etching process by the two-layer film resist method including the resist film of the present invention is completed by the peeling operation of the resist film. Peeling of this resist layer can be performed by simply dissolving the organic polymer material of the first layer. Since the organic polymer material is any photoresist and no alteration (curing or the like) occurs in the photoetching operation, the organic solvent of each known photoresist itself can be used. Or it can also peel without using a solvent by processing, such as plasma etching.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

Synthesis of Resin (1)

The monomer, methyl acrylate, t-butyl acrylate and maleic anhydride corresponding to the repeating unit (II-8) of the present invention are charged to the reaction vessel at a molar ratio of 15/10/35/40, and dissolved in tetrahydrofuran. , A solution of 50% solids was prepared. It was heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 15 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into a large amount of hexane to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (1) as a target product.

When molecular weight analysis was performed by GPC of the obtained resin (1), it was 13400 (weight average) in terms of polystyrene. The composition of the resin (1) based on the NMR spectrum was a molar ratio of the repeating unit (II-8) / maleic anhydride / methylacrylate (repeat unit 1) / t-butyl acrylate (repeat unit 2) of the present invention. 14/41/10/35.

Resin (2)-(12) of the said structure was synthesize | combined by the method similar to the synthesis | combination of the said resin (1). In addition, the composition ratio (molar ratio) of each repeating unit in resin (2)-(12) is shown in following Table 1.

Synthesis of Resin (1 ')

Monomer, norbornene and maleic anhydride corresponding to the repeating unit (III-7) of the present invention were injected into the reaction vessel at a molar ratio of 35/15/50, dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. It was. It was heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, the reaction was initiated by adding 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. After heating for 20 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into a large amount of hexane to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (1 ') as a target.

When molecular weight analysis was performed by GPC of obtained resin (1 '), it was 8700 (weight average) in terms of polystyrene. In addition, the composition of resin (1 ') by NMR spectrum was 36/50/14 in molar ratio of repeating unit (III-7) / maleic anhydride / norbornene (alicyclic olefin type repeating unit) of this invention.

Resin (2 ')-(16') of the said structure were synthesize | combined by the method similar to the synthesis | combination of the said resin (1 '). In addition, the composition ratio (molar ratio) of each repeating unit in resin (2 ')-(16') is shown in following Table 2.

Examples 1a to 28a and Reference Examples 1a to 2a

Preparation and Evaluation of Positive Resist Composition of First Form

2 g of the resin synthesized in the synthesis example, respectively, as shown in Table 3, 120 mg of the PAG (4-6), 8 mg of the organic basic compound and 5 mg of the surfactant as a photoacid generator were added, respectively, in a proportion of 10% by weight of solids. It was dissolved in propylene glycol monoethyl ether acetate (PGMEA), filtered through a 0.1 micron microfilter, and the positive resist compositions of Examples 1a to 28a were prepared.

In addition, a positive resist composition was prepared in the same manner as in Examples 1a and 13a except that the organic basic compound and the surfactant were not used as Reference Examples 1a to 2a.

The surfactant used is as follows.

W-1: Megafac F176 (product of Dainippon Ink Corporation) (fluorine system)

W-2: Megafac R08 (manufactured by Dainippon Ink Industries, Ltd.) (fluorine-based and silicon-based)

W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-4: Polyoxyethylene nonyl phenyl ether

The organic basic compound is as follows.

1: DBU (1,8-diazabicyclo [5,4,0] -7-undecene)

2: 4-DMAP (4-dimethylaminopyridine)

3: TPI (2,4,5-triphenylimidazole)

Evaluation test

FHi-028D resist (manufactured by FUJIFILM ORIN, i-line resist) was applied to the silicon wafer using Canon Coater CDS-650, and baked at 140 DEG C for 90 seconds to obtain a uniform film having a thickness of 0.83 mu m. . When this was heated at 200 ° C. for 3 minutes, the film thickness was 0.71 μm. The resist liquid adjusted as above was apply | coated, and it baked at 90 degreeC and 90 second, and apply | coated and formed into the film thickness of 0.20 micrometer.

The wafer thus obtained was exposed while the resolution mask was mounted on an ArF excimer laser stepper while varying the exposure amount and focus. Thereafter, the mixture was heated at 130 ° C. for 90 seconds in a clean room, and then developed for 60 seconds with a tetramethylammonium hydroxide developer (2.38%), rinsed with distilled water, and dried to obtain a pattern.

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows.
The results of these evaluations are shown in Table 3.

[Sensitivity Fluctuation Rate]: The sensitivity (exposure amount before preservation) after the liquid structure was evaluated as described above for the positive photoresist composition solution (coating solution) prepared as described above, and the composition solution was left at 23 ° C. for 1 week. The sensitivity (exposure amount after storage) was evaluated, and the sensitivity variation rate was evaluated by the following formula.

% Change in sensitivity = {(exposure amount before storage)-(exposure amount after storage)} / (exposure amount before storage) × 100

[Difference Dependence]: In the line and space pattern (dense pattern) and the isolated line pattern (coarse pattern) having a line width of 0.15 mu m, a range where the depth of focus allowing 0.15 mu m ± 10%, respectively, was overlapped. The larger this range, the better the density dependency.

As shown in Table 3, the positive photoresist composition of the first aspect of the present invention was found to have excellent resolution, good time-lapse storage stability of the composition solution, and excellent roughness dependency.

Examples 1b to 28b, Reference Examples 1b and 2b and Comparative Examples 1b to 6b

Preparation and Evaluation of Positive Resist Composition of Second Form

150 g of the photoacid generator shown in 2 g, Tables 4 and 5, 15 mg of the organic basic compound shown in Tables 4 and 5, and Tables 4 and 5, as shown in Tables 4 and 5, respectively, 10 mg of the surfactant as described in the above was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a solid content of 10% by weight, respectively, and then filtered through a 0.1 μm microfilter to prepare the positive resist composition of Examples 1b to 28b. It was.

In addition, as Reference Examples 1b and 2b and Comparative Examples 1b to 6b, as shown in Table 5, a positive resist composition without using a photoacid generator of the second form was prepared in the same manner as in Examples 1b to 28b.

Surfactants 1, 2, 3, and 4 are the same as W-1, W-2, W-3 and W-4 used in the above examples, respectively. 5 is Troisol S-336 (Troy Chemical Co., Ltd.).

Organobasic compounds 1, 2 and 3 are the same as in the above examples.

Evaluation test

FHi-028D resist (manufactured by FUJIFILM ORIN, i-line resist) was applied to the silicon wafer using Canon Coater CDS-650, and baked at 140 DEG C for 90 seconds to obtain a uniform film having a thickness of 0.83 mu m. . This was further heated at 200 ° C. for 3 minutes, and the film thickness was 0.71 μm. The resist liquid adjusted as above was apply | coated, and it baked at 140 degreeC and 90 second, and apply | coated to the film thickness of 0.20 micrometer.

The wafer thus obtained was exposed while the resolution mask was mounted on an ArF excimer laser stepper while varying the exposure amount and focus. Thereafter, the mixture was heated at 130 ° C. for 90 seconds in a clean room, and then developed for 60 seconds with a tetramethylammonium hydroxide developer (2.38%), rinsed with distilled water, and dried to obtain a pattern.

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows.

The evaluation results are shown in Tables 4 and 5.

[Sensitivity]: Sensitivity is the relative exposure amount when the exposure amount which reproduces the contact hole size of 0.18 micrometer of pitch width 1/1 as the sensitivity, and the exposure amount of the resist of Example 1 was set to 1.0 (other resist exposure amount / The exposure dose of Example 1b).

[Resolution power]: The resolution of the contact hole is expressed by the limit contact hole size (μm) resolvable at an exposure amount which reproduces a contact hole size of 0.18 μm with a pitch width of 1/1.

[Number of Particles and Increased Number of Particles after Preservation with Time]: The positive photoresist composition solution (coating solution) prepared as described above was allowed to stand for 1 week after the liquid structure (particle initial value) at 23 ° C. (hour The number of particles in the liquid of the number of particles after elapsed) was counted by a particle counter manufactured by Leon Corporation. Along with the particle initial value, the particle increase number calculated in (number of particles after time)-(particle initial value) was evaluated.

delete

As shown in Tables 4 and 5, the positive photoresist composition of the second aspect of the present invention is excellent in the resolution of contact holes. In terms of storage properties, the change in the time-lapse (particle increase) is particularly small at 23 ° C.

Examples 1c to 96c, Reference Examples 1c to 6c and Comparative Example 1c

Preparation and Evaluation of Positive Resist Compositions of Third Form

As shown in Tables 6 to 12, the resin synthesized in the above Synthesis Example was shown in 2 g, 140 mg of the photoacid generator shown in Tables 6-12, 12 mg of the organic basic compound shown in Tables 6-12, and Tables 6-12, respectively. The positive resist composition of Examples 1c-96c was prepared by mix | blending 10 mg of surfactant described above, melt | dissolving in the solvent shown in Tables 6-12 at the ratio of 10 weight% of solid content, respectively, and then filtering by the 0.1 micrometer microfilter.

In addition, as Reference Examples 1c to 6c and Comparative Example 1c, positive resist compositions without using a specific solvent of the third embodiment were prepared in the same manner as in Examples 1c to 96c.

As a solvent

S1: Propylene Glycol Monomethyl Ether Acetate

S2: Propylene Glycol Monomethyl Ether Propionate

S3: ethyl lactate

S4: Butyl Acetate

S5: 2-heptanone

S6: Propylene Glycol Monomethyl Ether

S7: ethoxyethyl propionate

S8: γ-butyrolactone

S9: ethylene carbonate

S10: Propylene Carbonate

S11: cyclohexanone

Surfactants 1, 2, 3, and 4 are the same as W-1, W-2, W-3, and W-4 used in the above examples, respectively. 5 is Troisol S-336 (Troy Chemical Co., Ltd.).

Organobasic compounds 1, 2, and 3 and PAG7-1 and 7-2 are the same as those used in the above examples.                     

Evaluation test

FHi-028D resist (manufactured by FUJIFILM ORIN, i-line resist) was applied to the silicon wafer using Canon Coater CDS-650, and baked at 140 DEG C for 90 seconds to obtain a uniform film having a thickness of 0.83 mu m. . This was further heated at 200 ° C. for 3 minutes, and the film thickness was 0.71 μm. The resist liquid adjusted as above was apply | coated, and it baked at 130 degreeC and 90 second, and formed it into the film thickness of 0.20 micrometer.

The wafer thus obtained was exposed while the resolution mask was mounted on an ArF excimer laser stepper while varying the exposure amount and focus. Thereafter, the mixture was heated at 130 ° C. for 90 seconds in a clean room, and then developed for 60 seconds with a tetramethylammonium hydroxide developer (2.38%), rinsed with distilled water, and dried to obtain a pattern.

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope, and the resist was evaluated as follows.

The results of these evaluations are shown in Tables 13-19.

[Edge Roughness]: The edge roughness was measured using a side scanning scanning electron microscope (SEM) to determine the edge roughness of a 0.14 µm line and space (line / space = 1 / 1.2) pattern. It is more preferable that the line pattern edge is detected at a plurality of positions in the measurement monitor, and the nonuniform dispersion degree (3σ) of the detection position is an index of the edge roughness, and the smaller the value is, the more preferable.

[Number of Particles and Increased Number of Particles after Preservation with Time]: After the liquid composition (initial particle value) and left for 1 week at 4 ° C for the positive photoresist composition solution (coating solution) prepared as described above (hours) The number of particles in the liquid of the number of particles after elapsed) was counted by a particle counter manufactured by Leon Corporation. Along with the particle initial value, the particle increase number calculated in (number of particles after time)-(particle initial value) was evaluated.

As shown in Tables 13 to 19, the positive photoresist composition of the third aspect of the present invention showed excellent performance throughout the evaluation items.

Also, in Reference Examples 5 and 6, the storage time was set to 23 ° C., and storage stability was similarly evaluated. In Reference Example 5, the initial particle size was 15, the number of particles was increased, The initial value was 20 and the number of particle increase was 55.

The present invention provides a positive photoresist composition having a high resolution of 0.15 µm or less, having a good time-lapse storage stability of the composition solution, and excellent density-dependency, high sensitivity, and having a high sensitivity of 0.15 µm or less in the manufacture of a semiconductor device. It is possible to provide a positive photoresist composition having a resolution and having good time-lapse storage stability of the composition solution, an edge roughness of the resist pattern, and excellent storage stability.

Claims (11)

(A) a compound which generates an acid by irradiation of actinic light or radiation, (B) a resin having a partial structure represented by the following general formula (I), and having increased solubility in an alkaline developer by the action of an acid; (C) an organobasic compound, and (D) A positive photoresist composition comprising at least one of a fluorine-based surfactant and / or a silicone-based surfactant and a nonionic surfactant.

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) The positive photoresist composition according to claim 1, wherein the resin (A) having increased solubility in an alkaline developer by the action of an acid contains a repeating unit represented by the following general formula (II).

(In formula (II), R ¹ to R ⁷ and m are as defined in formula (I). Y ¹ represents a hydrogen atom, a methyl group, a cyano group or a chlorine atom. L ¹ represents a single bond or a divalent compound. Display the connector.) The positive photoresist composition according to claim 1, wherein the resin (A) in which the solubility in an alkaline developer is increased by the action of an acid contains a repeating unit represented by the following general formula (III).

(In formula (III), R ¹ to R ⁷ and m are as defined in formula (I). M ¹ together with the two carbon atoms bonded to form an alicyclic structure which may have a substituent) Represents an atomic group, n represents 1 or 2. L ² represents a single bond or an n + monovalent linking group, one side of which is connected to a carbon atom forming a ring) (A) A sulfonium salt compound which produces an acid by irradiation of actinic light or radiation represented by general formula (PAG4), and (B) A positive photoresist composition, comprising a resin having a partial structure represented by the following general formula (I) and increasing solubility in an alkaline developer by the action of an acid.

(In General Formula (PAG4), Rs1 to Rs3 each independently represent an alkyl group which may have a substituent and an aryl group which may have a substituent. In addition, two of Rs1-Rs3 may be couple | bonded through each single bond or a substituent. Z ^- represents a pair ion.)

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) The positive photoresist composition according to claim 4, wherein the sulfonium salt compound of (A) is a compound represented by the following general formula [sI] and generates an acid by irradiation with actinic light or radiation.

(In general formula [sI], Rs4 to Rs6 are each independently an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, and an alkoxycarbonyl group which may have a substituent. And the acyl group which may have a substituent, the acyloxy group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group, and a carboxyl group. l: 1 ~ 5 m: 0-5 n: 0 to 5 are displayed. When l + m + n = 1, Rs4 has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent The acyl group which may be used and the acyloxy group which may have a substituent are shown. X: R-SO ₃ , R is an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent.) (A) a compound which generates an acid by irradiation of actinic light or radiation, (B) a resin having a partial structure represented by the following general formula (I), and having increased solubility in an alkaline developer by the action of an acid; (E) containing at least one selected from the following solvent A group, at least one selected from the following solvent B group, or at least one selected from the solvent A group and at least one selected from the following solvent C group Mixed solvent Group A: propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactic acid and alkoxyalkyl propionate Group C: A positive photoresist composition comprising γ-butyrolactone, ethylene carbonate and propylene carbonate.

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) (A) a compound which generates an acid by irradiation of actinic light or radiation, (B) a resin having a partial structure represented by the following general formula (I), and having increased solubility in an alkaline developer by the action of an acid; (E) A mixed solvent containing at least one member selected from the following solvent A group, at least one member selected from the following solvent B group, and at least one member selected from the following solvent C group Group A: propylene glycol monoalkyl ether alkoxylate Group B: propylene glycol monoalkyl ether, alkyl lactic acid and alkoxyalkyl propionate Group C: A positive photoresist composition comprising γ-butyrolactone, ethylene carbonate and propylene carbonate.

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) (A) a compound which generates an acid by irradiation of actinic light or radiation, (B) a resin having a partial structure represented by the following general formula (I), and having increased solubility in an alkaline developer by the action of an acid; (E) A positive photoresist composition comprising at least one kind of alkyl lactate and a mixed solvent containing at least one kind of an ester solvent and an alkoxyalkyl propionate.

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) (A) a compound which generates an acid by irradiation of actinic light or radiation, (B) Resin which has the partial structure represented by following General formula (I), and whose solubility to alkaline developing solution increases by the action of an acid, and (E) A positive photoresist composition comprising a solvent containing heptanone.

(In formula (I), m represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may be bonded to each other to form a cyclic alkyl group. R ³ and R ⁴ may each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may be bonded to each other to form a cyclic alkyl group, wherein R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, Trialkylsilyl group or trialkylsilyloxy group.) The positive photoresist composition according to claim 9, wherein the solvent (E) further contains at least one of propylene glycol monoalkyl ether, alkyl lactate, and alkoxyalkyl propionate. The positive photoresist composition according to any one of claims 8 to 10, wherein the (E) solvent further contains one or more of γ-butyrolactone, ethylene carbonate, and propylene carbonate.