TW200534042A - Positive resist composition for immersion exposure and method for forming pattern using the same - Google Patents

Abstract

The purpose of the present invention relates to provide a positive resist composition for immersion exposure which has board range of exposure, small relation of the display time and are useful the immersion exposure. The resolving method of the present invention relates to a positive resist composition for immersion exposure and a method for forming pattern using the same. The positive resist composition for immersion exposure is characterized in that comprises (A) a resin having aliphatic hydrocarbon structure with monocyclic ring or polycyclic ring, 1.0001~0.005 m equivalent of OH value and the solubility for the alkali solution could be enhanced by applying acid treatment; (B) a compound which the acid could be produced by irradiating active light or radioactive ray.

Description

200534042 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a semiconductor manufacturing process such as 1C, the manufacture of circuit substrates such as liquid crystals, hot needles, and other photolithography processes used in photoresist applications. Positive type photoresist composition and pattern forming method using the same. In particular, a positive photoresist composition suitable for exposure by a liquid immersion projection exposure apparatus using far-ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same. β [Prior art] '' Shortening the wavelength of exposure light sources with the miniaturization of semiconductor elements and high opening number (high NA) of projection mirrors. Currently, NA0.84 with ArF excimer laser with a wavelength of 193nm has been developed. Exposure machine. These can be expressed by the following conventional formula. (Resolution) = k! · (Λ / ΝΑ) (focus depth) = ± k2 · λ / ΑΝ2 I where λ is the wavelength of the exposure light source, NA is the number of openings of the projection mirror, k «and k2 are the coefficients of the relevant process . In addition, we reviewed the exposure machine that uses high-resolution FW excimer laser with a wavelength of 157nm as the light source for short-wavelength shortening, but it is only used for the lens material and photoresist used in the exposure device for short-wavelength It is very limited, so it is extremely difficult to stabilize the manufacturing cost or quality of the device or raw materials. There is no possibility of an exposure device and photoresist that have sufficient performance and stability at the same time in the required period. A technique for improving the resolution in an optical microscope has conventionally been filled with a high refractive index liquid (hereinafter referred to as a "liquid immersion liquid") between a projection lens 200534042 and a sample. The so-called liquid immersion method is known. The "liquid immersion effect" is λ0 is the wavelength of the exposure light source in the air, η is the refractive index of the liquid immersion liquid for air, β is the half-angle of the light beam, and NAo = sin Θ The resolution and depth of focus are expressed by the following formulas. (Resolution) = k! · (Λ〇 / η) ΝΑ〇 • (focus depth) = soil k2 · (λ〇 / η) / ΝΑ〇2 In other words, the liquid immersion effect is equal to the exposure wavelength of the use wavelength of 1 / η . When the projection optical system is the same NA, the focal depth can be η times by liquid immersion. This system is extremely effective for the shape of the pattern. In addition, the super-resolution technology that can be combined with the phase shift method and anamorphic illumination method is currently under review. Examples of devices that apply this effect to the transfer of fine patterns of semiconductor elements include Patent Document 1 (Japanese Patent Publication No. 5 7-1 5 343 3), Patent Document 2 (Japanese Patent Application Laid-Open No. 7-220990), and the like. However, the photoresist of the suitable φ liquid immersion exposure technology is not discussed. In Patent Document 3 (Japanese Patent Application Laid-Open No. 10-303 1 14), it is indicated that the refractive index change of the liquid immersion liquid causes a difference in the wave surface of the exposure machine and causes deterioration of the projection image. Therefore, the refractive index of the liquid immersion liquid is controlled. It is extremely important to reveal that a suitable liquid immersion liquid is water in which the temperature coefficient of the refractive index of the liquid immersion liquid is controlled to a certain range, or an additive that reduces surface tension or increases interfacial activity is added. However, 'there is no disclosure of additives or discussion of photoresist used in liquid immersion exposure techniques. 200534042 Recently, non-patent literature 1 (SPIEProc 4688, 11 (2002)) and non-patent literature 2 (J. Vac. Sci · Tecnol. B 1 7 (1 99)) have reported reports on liquid immersion exposure technology. When an ArF excimer laser is used as the light source, pure water (refractive index of 193 nm is 1.44) is used as the liquid immersion liquid in terms of processing safety and transmittance and refractive index of 193 nm. When an F2 excimer laser is used as the light source, the fluorine-containing solution is discussed from the balance between the transmittance and the refractive index of 157 nm, but sufficient ones have not been found in terms of environmental safety or refractive index. The earliest _ The liquid immersion exposure technology considering the degree of liquid immersion effect and the completeness of the photoresist is mounted on the ArF exposure machine. After using KrF excimer laser (248nm) photoresist to compensate for the decrease in sensitivity due to light absorption, a chemically enlarged image formation method was used as the photoresist image formation method. Taking an example of a positive-type chemically enlarged image formation method as an example, the acid generator in the exposed part is decomposed to generate an acid by exposure, and the post-exposure baking (PEB: post-exposure baking) is used as a reaction. A method in which an alkali-insoluble group is changed to an alkali-soluble group by a catalyst, and the exposed portion is removed by an alkali-developed φ image to form an image. In the liquid immersion exposure, the photoresist film and the optical lens are filled with an immersion liquid (also referred to as a liquid immersion liquid), and the photomask is transferred to the photoresist film through a photomask exposure. It is predicted that the impregnating solution will be affected by the chemical reaction (acid-catalyst-type deprotection reaction, development reaction) caused by the inside of the photoresist during or after exposure, because it penetrates the inside of the photoresist film. However, the extent or institution of the impact remains uncertain. When the chemically amplified photoresist is used in liquid immersion exposure technology, the acid on the surface of the photoresist produced during 200534042 during exposure moves in the liquid immersion liquid, which changes the acid concentration on the surface of the exposed part. This is the biggest problem when the chemically amplified positive photoresist was developed. The post exposure time delay (PEB: Post Exposure time Delay) between the τ ^ -PEB is caused by the trace amount of alkaline pollution at the ppb level in terms of the environment. The phenomenon of acid inactivation on the exposed surface is very similar, but the effect or mechanism of the liquid immersion exposure by photoresist is still unclear. For example, when a chemically amplified photoresist liquid immersion exposure that is not problematic in lithography is generally exposed by exposure, it is necessary to improve the deterioration of the exposure range and the correlation of development time. The exposure range is the width that allows the exposure amount to vary when a predetermined pattern is formed. The larger the exposure range, the better the performance is less susceptible to changes in exposure. The development time dependence refers to the degree of change in the size of the pattern by the development time. The greater the correlation of the development time, the worse the dimensional uniformity within the wafer surface, and the controllability of the process becomes difficult. [Patent Document 1] Japanese Patent Publication No. 57-1 5 34 3 3 [Patent Document 2] Japanese Patent Publication No. 7-220990 [Patent Document 3] Japanese Patent Publication No. 10 — 303114 [Non-Patent Document 1] International Proceedings of the Optical Engineering Society (Proc, SPIE), 2002, Vol. 468, Vol. 8, page 11 [Non-Patent Document 2] J. Vac. Sci. Tecnol. B 17 (1999) [Summary of the Invention] The object of the present invention is In view of the problems of the above-mentioned conventional technology, a positive photoresist composition having a wide exposure range and a small correlation of development time and suitable for liquid immersion exposure is provided. 200534042 The present invention is a positive type photoresist composition for liquid immersion exposure with the following constitution, thereby achieving the above-mentioned object of the present invention. (1) A positive photoresist composition for liquid immersion exposure, characterized by containing (A) an alicyclic hydrocarbon structure having a monocyclic or polycyclic ring, and having an OH valence of 0.000 1 to 0.005 milli-equivalent, increased by the action of an acid Resin having a large solubility in an alkali developer, and (B) a compound that generates an acid by irradiation with active light or radiation. (2) A pattern forming method, characterized in that a photoresist film is formed from the positive-type photoresist composition described in the above (1), and the photoresist film is subjected to liquid immersion exposure and development. [Effects of the Invention] The present invention can provide a positive type photoresist composition which is not easily affected by changes in exposure and development processing conditions such as exposure amount and development time, and is suitable for liquid immersion exposure, and a pattern forming method using the same. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. In addition, in the description of the radicals (atomic groups) in the present invention, there is no description that when substituted and unsubstituted, it includes those having no substituents and those having substituents. For example, "alkyl" includes unsubstituted alkyl (unsubstituted alkyl) and substituted alkyl (substituted alkyl). [1] Resin that increases solubility in alkaline imaging solution by acid action Resin (referred to as acid decomposition) that increases the solubility in alkaline imaging solution by the acid action contained in the positive composition for liquid immersion exposure of the present invention (A)), 0H valence is 0.000 1 to 0.005 milliequivalents, and has a monocyclic or polycyclic alicyclic hydrocarbon structure 200534042 [acid decomposable group] Furthermore, the positive photoresist composition for liquid immersion exposure of the present invention The contained resin is a resin (acid-decomposable resin) which increases the solubility of the alkali developing solution by the action of acid, and contains a repeating unit of a base (acid-decomposable group) which is decomposed by the action of acid to generate an alkali-soluble group. Examples of the alkali-soluble group include a hydroxyl group, a carboxyl group, and a sulfonic acid group. The acid-decomposable group may exist in the main chain or side chain of the resin, or both the main chain and the side chain. The most preferable group among the acid-decomposable groups is a group in which a hydrogen atom of a -COOH group is substituted with an acid-dissociated group. Examples of the acid-decomposable group include a cumyl group, an enol ester group, an acetal ester group, and a tertiary ester group. Preferred are esters of tertiary hospitals and the like. An acid-decomposable group which the acid-decomposable resin (A) may have, for example

OC (R30) (R37) < Rsa), 〇-C (R36) (R37) (OR39), -〇-C (== ^ 0) -〇-C (R36) (R37) (R3B), -O-C (Rcu) (Roz) (OR material), surface OC (R01) (R〇2) -C-0) -O-C (R36) (P, s7). (R38) and so on. In the formula, each of R36 to R39 represents an independent alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R36 and R37, R36 and R39 can be bonded to each other to form a ring. R (H ~ R02) each represents an independent hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Moreover, -C (R36) (R37) (R38) refers to a carbon atom Each of the groups shown by R36 to R39 above is a single bond group. The same applies to the following. The content of the repeating unit having an acid-decomposable group in the acid-decomposable resin (A) is 10 in all the repeating units. ～ 70 mol% is preferable, more preferably -10- 200534042 20 to 65 mol%, and the most preferable is 25 to 50 mol%. [OH value] The acid contained in the positive type photoresist composition of the present invention The OH value of the decomposable resin (8) is 0.0001 to 0.005 milli-equivalent, preferably 0.0001 to 0.003 milli-equivalent, and more preferably 0.0001 to 0.002 milli-equivalent. In the present invention, the OH valence means lg acid decomposable resin The molar equivalent of OH. In other words, the OH valence can be obtained by the number of OH groups / molecular weight. For example, the molecular weight of vinyl alcohol unit (-CH2-CH (OH)-) is 44, because it has one OH group, OH The valence is 1/44 equivalent. In order to obtain an acid decomposable resin (A) having an OH value of 0.0001 to 0.005 milliequivalents, a repeating unit containing an OH group (hydroxyl group) may be introduced into the resin. Containing OH The repeating unit of the base may be a repeating unit having one or more OH groups. The acid-decomposable resin (A) may contain two or more repeating units having one or more OH groups. The repeating unit containing an OH group is OH The repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon structure is preferable, and the repeating unit having an OH group directly bonded to the alicyclic hydrocarbon structure is more preferable. In order to make the OH value of the acid-decomposable resin (A) be 0.0001 to At 0.005 milliequivalents, depending on the molecular weight of the monomer, the number of OH in the repeating unit, and the proportion of repeating units with OH groups in all repeating units is 1 to 70 mole%. Specific examples of repeating units containing OH groups are as follows Those shown are not limited by these specific examples. -11- 200534042

-fc% ·

OH

12 200534042 [Monocyclic or polycyclic alicyclic hydrocarbon structure] The acid-decomposable resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure. The acid-decomposable resin (A) contains at least one kind of repeating unit selected from a group having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pi) to general formula (PVI) and the general formula (II-AB) The repeating units shown are preferred as repeating units having a monocyclic or polycyclic alicyclic hydrocarbon structure. First, the structure of a part containing an alicyclic hydrocarbon represented by the general formula (pi) to the general formula (PVI) will be described.

(PD

(pM) 200534042

R21 (piv) ^ 22 ί? 23 〇 I I ii

G-CH-C- R

(pV) 24 R25

—C—O—C \ In the formula, Rm represents a methyl group, an ethyl group, a group, an isobutyl group, or a 2-butyl group, and Z represents an atomic group necessary for a group. R12 to R16 each represent an independent carbon number group or an alicyclic hydrocarbon group, but at least one of R12 to R14 is an alicyclic hydrocarbon group. Ri7 to R21 each represent an independent hydrogenogen or a branched alkyl group or an alicyclic hydrocarbon group, but R ring hydrocarbon groups. Any of R19 and R21 is a branched alkyl group or an alicyclic hydrocarbon group. \ z (pVI) n-propyl, isopropyl, n-butyl carbon atoms and one to four alicyclic hydrocarbons, one linear or branched alkane, or any of Rl5 and R16, and 1 to 4 carbons At least one of the linear 17 to R21 is fat. The carbon number is 1 to 4 linear. -14- 200534042 R22 to R25 each represents an independent hydrogen atom, and the carbon number is 1 to 4 linear or branched. An alkyl group or an alicyclic hydrocarbon group, but at least one of Rn to R25 represents an alicyclic hydrocarbon group. R23 and R may be bonded to each other to form a ring. The alicyclic hydrocarbon group of R M to R 2 5 or the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specifically, for example, it has a monocyclic, bicyclic, tricyclic, tetracyclic structure having a carbon number of 5 or more. The carbon number is preferably 6 to 30, and more preferably 7 to 25 carbons. These alicyclic hydrocarbon groups may have a substituent. Preferred alicyclic hydrocarbon groups are adamantyl, normantyl, decalinyl, tricyclodecyl, tetracyclododecyl, norbornenyl, cedarenol, cyclohexyl, cycloheptyl , Cyclooctyl, cyclodecyl, cyclododecyl. More preferred are adamantyl, decalinyl, norbornenyl, cedarenol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. Examples of such alicyclic hydrocarbon groups include alkyl groups, halogen atoms, hydroxy groups, oxo groups, residues, and oxo groups. The fluorenyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and the like, and more preferably selected from methyl, ethyl, propyl, and isopropyl. The alkoxy group is, for example, one having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The above-mentioned alkyl, alkoxy, alkoxycarbonyl and the like may further have substituents such as a hydroxyl group, a halogen atom, and an alkoxy group. These resins have a structure represented by the general formulae (pi) to (PVI) and can be used for protecting alkali-soluble groups. The alkali-soluble group is, for example, various groups known in the art. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol, and a carboxylic acid -15-200534042 group and a sulfonic acid group are preferred. The structure in which the alkali-soluble base group protected by the structure represented by the general formulae (pI) to (pVI) of the above resin is substituted with the hydrogen atom of the residue by the structure represented by the general formulae (Pi) to (PVI) is preferable. For example, a repeating unit represented by the following general formula (PA) is preferred.

R

(pA) 0 wherein R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms (a substituted alkyl group, particularly a fluorine-substituted alkyl group). Several Rs may be the same or different. A is a single bond, alone or two or more selected from the group consisting of alkylene, ether, thioether, carbonyl, ester, amido, amido, carbamate, or urea The base.

Ra represents any one of the formulae (pi) to (pVI). The repeating unit represented by the general formula (pA) is preferably the repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate . The following are specific examples of the repeating unit represented by the general formula (PA). 200534042

23 The unit having an alicyclic hydrocarbon structure is, for example, the following repeating unit. -17- 200534042

Next, the alicyclic complex having the general formula (II-AB) will be described. cf3-OH CFa structure weight

In the formula (II-AB): ^^ 'and R12' each represent an independent hydrogen atom, a cyano group, or an alkyl group. The Z 'system contains two carbon atoms (C-C) bonded together, and is represented as an atomic group at the time of construction. The repeating unit represented by the general formula (Π-AB), and the repeating unit represented by the formula (Π-A) or the general formula (π · B) is preferred. Halogen atom or alicyclic system is as follows -18- 200534042

⑴-B) • In the formulae (II-A) and (II-B): R13, ~ R16, each represents an independent hydrogen atom, halogen atom, meridian, cyano, -COOH, -COORs, A group decomposed by the action of an acid, -COCO-X-A'R ^, a radical or a cyclic hydrocarbon group. Here, R5 represents a radical, a cyclic hydrocarbon group, or a group described below. The X system represents an oxygen atom, a sulfur atom, -ΝΗ-, -NHS〇2, or -NHs〇2NH-A 'represents a single bond or a divalent bonding group. Further, at least two of RI3, ~ R16 'may be bonded to form a ring. n means ⑩ or 1. R17 'represents -COOH, -C00R5, -CN, meridian, alkoxy, -CO-NH-R6, -CO-NH-SOpL ^ and the following groups. R6 represents a radical or a cyclic hydrocarbon group. -Y base: 200534042

In the -Y group, R21 'to R30' each represent an independent hydrogen atom or an alkyl group. 3 and b represent 1 or 2. In the general formulae (pi) to (pVI), the radicals of R12 to R25 represent straight or branched chain alkyl groups having 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, and the like. In addition, the substituent that each of the alkyl groups may have, for example, 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a fluorenyl group, a fluorenyl group, a cyano group, Jingji, Junji, Yuanjiji, nitro, etc. In the general formula (II-AB), 1111 'and R! 2' each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group. $ Z 'is a bond containing two carbon atoms (C-C), and is expressed as an atomic group when forming an alicyclic structure. Examples of the halogen atom of ^^ and R12 'include a chlorine atom, a bromine atom, a gas atom, and an iodine atom. The aforementioned Rll ', Rl2', R21 'to R3. 'The courtyard base is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or $ chain alkyl group having 1 to 6 carbon atoms, and the most preferred is Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Other substituents of the above-mentioned alkyl group include, for example, a hydroxyl group, a halogen atom, a Jun-20-200534042 group, an alkoxy group, a fluorenyl group, a cyano group, a fluorenyl group, and the like. Halogen atom, bromine atom, fluorine atom, iodine atom, etc., alkoxy groups such as ethoxy group, propoxy group, butoxy group and the like having 1 to 4 carbon atoms, fluorenylmethyl, ethyl, etc. An example of the oxy group is ethoxy. The atomic group for forming the alicyclic structure of Z ′ is a bridged atomic group for forming an atom of a repeating unit of an alicyclic hydrocarbon which may have a substituent and forming a repeating unit of a bridged alicyclic hydrocarbon. Better. The structure of the alicyclic hydrocarbon formed is, for example, the same as the alicyclic hydrocarbon group of the general formula (pi) to Rm to R25. The alicyclic hydrocarbon may have a substituent in its structure. R13 'to R16 in the general formula (II-A) or (II-B). Among the above-mentioned repeating units having a bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable. In the repeating unit represented by the general formula (II-AB), the acid-decomposable group in the above _〇 (= 〇) 7-octa'-1 ^ 7 'includes an alicyclic substituent which forms 2'. The structure of the acid-decomposable group is-C (= 0) -Xi-R. Means. In the formula, R0 includes, for example, 3-isobornyl such as 3-butyl and 3-pentyl, 1-ethoxyethyl, 1-butoxyethyl, and 1-isobutyl 1.cyclohexyl 1-alkoxyethyl such as oxyethyl, alkoxymethyl such as 1-methoxymethyl 3-methyl, etc., 3-carbonylalkyl, tetrahydropyran: furyl, trialkylmethyl Silyl ester group, 3-carbonylcyclohexyl ester group: For example, there is a chloromethoxy group, and for example, there is a group in a resin, and examples of the substituents in the alicyclic structure "(PVI) are also included in the structure as above Alkyl, I-ethyl, I, 1-ethoxy, tetrahydro 2-methyl-2--21-200534042 adamantyl, mevalonolactone residues, etc. Xl is synonymous with X above. The halogen atom of R13 '~ R16' includes, for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. The alkyl groups of the aforementioned R5, R6, R13 '~ R16, having 1 to 10 carbon atoms are linear or branched. A chain alkyl group is preferred, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and the most preferred are methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl Group, 2-butyl group, 3-butyl group, etc. R5, R6, R! 3 '~ R i6 Examples of cyclic hydrocarbon groups include cyclic alkyl groups, bridged tobaccos such as cyclopropyl, transpentyl, cyclohexyl, adamantine, 2-methyl-2-adamantine, n-bornyl, and bornyl , Isobornyl, dicyclodecyl, dicyclopentyl, norbornyl epoxy, menthol, isomenthol, neomenthol, tetracyclododecyl, etc. At least R13 ′ ~ R〆 Two bonds are formed to form a ring, for example, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like having a carbon number of 5 to 12. The above-mentioned R ^ 's ethoxy groups include, for example, methoxy and ethoxy. 1 to 4 carbon atoms, such as a hydroxyl group, a propoxy group, a butoxy group, etc. The other substituents in the above-mentioned radicals, cyclic nicotyl radicals, and radicals include, for example, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, Fluorenyl, ^ ^ ^ wind, alkoxy, alkyl, cyclic hydrocarbon, etc. Halogen atoms are, for example, chlorine atoms, κ π ^ misatoms, gas atoms, iodine atoms, etc. Alkoxy groups are, for example, methoxy 1 to 4 carbon atoms, such as methyl, ethyl argonyl, propyl, propoxy, butoxy, and the like. Examples of fluorenyl include methylamino, ethyl, and ethoxy. Examples of fluorinated oxy include ethoxy. Base In addition, the cyclic hydrocarbon group is exemplified above. -22- 200534042 The above-mentioned A, the divalent bonding group, for example, alone or in combination of two or more, is selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, and an ester. Radicals of the general formula (II-A) or the general formula (II-B) of various substituents of r13, ~ r16, It is an atomic group when forming an alicyclic structure of the aforementioned general formula (II-AB) or a substituent of an atomic group Z having a bridged alicyclic structure. The general formula (II-A) or the general formula (II-A) Specific examples of the repeating unit shown in B) are as follows, but the present invention is not limited by these specific examples.

-23- 200534042

[Π-25]

b c {ch3j3 [11-23]

The acid-decomposable group in the acid-decomposable resin (A) having a monocyclic or polycyclic alicyclic hydrocarbon structure may be one having an alicyclic hydrocarbon containing an acyclic hydrocarbon having a general formula (pi) to general formula (pVI). Partially structured repeating units, repeating units represented by the general formula (II-AB), and repeating units of other copolymerization components described below. In addition, the 'acid-decomposable resin (A) preferably has a lactone group, and is more preferably φ. The repeating unit of the lactone structure base, the base having the lactone structure can be directly bonded to the main chain.

-24- 200534042

In the general formula (Lc), Ral, Rbl, Ru, Rdl, and Rei each represent an independent hydrogen atom or an alkyl group. m and n each represent an independent integer of 0 to 3, and m + n is 2 to 6. In the general formulae (III-1) to (III-5), Rib to R5b each represent an independent hydrogen atom and an alkyl group. , Cycloalkyl, alkoxy, alkoxycarbonyl, alkylsulfoimino, or alkenyl. Two of Rlb to R5b can be bonded to form a ring. An alkyl group of Ral ~ Rel in general formula (Lc) and an alkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfonylimino group in general formula (Πΐ-ΐ) ~ Rib of ~ (III- 5) The alkyl group includes, for example, a linear or branched alkyl group, and may have a substituent. Preferred substituents include, for example, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a fluorenyl group having 2 to 5 carbon atoms, and a fluorene having 2 to 5 carbon atoms. Oxygen, cyano, hydroxyl, carboxyl, alkoxycarbonyl with 2 to 5 carbons, nitro, etc. A repeating unit having a group having a lactone structure represented by any one of the general formula (Lc) or the general formula (in- 丨) to (III-5), for example, the above-mentioned general formula (1A) or (II) -BM R ^ '~ R16, at least one of which has a base represented by the general formula (Lc) or (III-1) ~ (III-5) (for example, <0; 5 之 & Formula (Lc) or a group represented by general formulae (III-1) to (111-5)), or a repeating unit represented by the following general formula (ai), etc. -25- 200534042

RbO (Al) 0 = 0 t 〇

• I A'-B2 In the general formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Rb. Preferred substituents which may be contained in the alkyl group are exemplified by the preferred substituents which the alkyl group in Rlb in the general formulae (III-1) to (III-5) has.

Examples of the halogen atom of RbQ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb. Argon is preferred. A 'represents a divalent group of a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a combination thereof. φ L represents a group represented by any one of the general formula (Lc) or the general formulae (III-1) to (III-5). The following are specific examples of repeating units having a base having a lactone structure, but the present invention is not limited thereto. (Where Rx is H, CH3 or CF3) -26- 200534042

-27- 200534042

-28-200534042

-29- 200534042

The acid-decomposable resin (A) may contain a repeating unit having a group represented by the following general formula (IV).

(IV) In the general formula (IV), R2. "~ R" each represents an independent hydrogen atom or a hydroxyl group. However, at least one of R 2. ~ R 4. represents a hydroxyl group. The group represented by the general formula (IV) is preferably a dihydroxy group or a monohydroxy group, and more preferably It is a dihydroxy compound. The repeating unit having a group represented by the general formula (IV) has, for example, at least one of Ri3 'to Ri6' in the general formula -30-200534042 (II-A) or (II-B). A group represented by the general formula (IV) (for example, R5 of -COOR 5 represents a group represented by the general formula (IV)), or a repeating unit represented by the following general formula (All).

(All) In the general formula (All), Ri. Represents a hydrogen atom or a methyl group. Each of ~ is a hydrogen atom or a hydroxyl group. But r2. At least one of ~ r4c is a hydroxyl group. R2. ~ R4. Of these, at least two are preferably hydroxyl groups. In the following, specific examples of repeating units having a structure represented by the general formula (All) are provided, but are not limited thereto.

The acid-decomposable resin (A) may contain a repeating unit represented by the following general formula (V). -31- (V) 200534042

In the general formula (V), Z2 represents -0- or -N (R4i). R4i represents a hydrogen atom, a hydroxyl group, an alkyl group, or -0SO2-R42. R42 represents an alkyl, cycloalkyl or camphor residue. The alkyl, cycloalkyl, and camphor residues of R41 and R42 may be substituted with a halogen atom (preferably a fluorine atom). • The repeating unit represented by the above general formula (V) is, for example, the following specific examples, but it is not limited thereto. — (Cm_cwj- — (ch_Crt)-— ^ h)-

. Shanghai C, N, C々0 〇 Shanghai 0, C, W, C ^ O f I f H 〇H CH3

Jinyi 丨 H— CFa

It is preferable that the acid-decomposable resin (A) is composed of only (meth) acrylic repeating units. The acid-decomposable resin (A) may contain, in addition to the above-mentioned repeating structural unit, resolution, heat resistance, and general necessary characteristics of the photoresist to adjust dry etching resistance or standard developer suitability, substrate adhesion, photoresist appearance, and photoresist. Various repeating structural units for the purpose of sensitivity etc. -32- 200534042 The repeating structural unit includes, for example, the following repeating structural unit of a monomer, but is not limited by these. This allows fine tuning of the properties required for acid-decomposable resins, in particular (1) solubility in coating solvents, (2) film-forming properties (glass transition points), (3) alkali developability, and (4) film edges. Selection of water-soluble and alkali-soluble groups) (5) Adhesion of the unexposed part to the substrate • (6) Dry etching resistance, etc. This monomer has, for example, an addition polymerizable property selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Saturated bond compounds, etc. The addition polymerizable unsaturated compound may be copolymerized with the monomers of the various repeating structural units described above, or may be copolymerized. φ In the acid-decomposable resin (A), the molar ratio of each repeating structural unit is used to adjust the photoresist's dry etching resistance or standard imaging solution suitability, substrate adhesion, photoresist appearance, and photoresist general Set the resolution, heat resistance, sensitivity, etc. of the required performance appropriately. The preferable aspect of the acid-decomposable resin (A) of this invention is as follows. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulae (pi) to (pVI) (side chain type) (2) Those containing a repeating unit represented by the general formula (II-AB) (Main chain type) -33- 200534042 However, in (2), for example, there are the following. (3) A repeating unit represented by the general formula (11-AB), a maleic anhydride derivative, and a (meth) acrylate structure (mixed type) The acid-decomposable resin (A) has the general formula (p I) The content of the repeating unit of the partial structure of the alicyclic hydrocarbon shown by (pv I) is preferably 20 to 70 mole% of the total repeating structural unit, more preferably 24 to 65 mole%, and the most preferable Those are 28 to 60 mol%. $ The content of the repeating unit represented by the general formula (II-AB) in the acid-decomposable resin (A) is preferably 10 to 60 mol%, and more preferably M to 55 mol% in all repeating structural units. The best is 20 to 50 mole%. In addition, based on the monomers of the other copolymerization components described above, generally, the content of the repeating structural unit in the resin is a repeating structure having a partial structure containing an alicyclic hydrocarbon represented by the general formula ~ (ρ VI). The total molar number of the unit and the repeating unit represented by the above general formula (Π-AB) is preferably 99 mol% or less, more preferably 90 mol% or less, and most preferably 80 mol%. the following. In addition, the content of the repeating unit having a lactone structure-based group and the stomach (hydroxyadamantane structure) represented by the general formula (IV) in the stomach are described below. The total number of repeating structural units having a partial structure containing an alicyclic hydrocarbon represented by the general formulae (pi) to (P VI) and the repeating unit represented by the general formula (II-AB) has The content of the repeating unit of the base of the lactone structure is preferably from 70 to 70 mole%, and more preferably from 10 to 70 mole%. -34- 200534042 The content of the repeating unit having a group represented by the general formula (IV) is preferably 1 to 70 mole%, and more preferably 1 to 50 mole%. When the composition of the present invention is for ArF exposure, it is preferable that the resin has no aromatic group in terms of transparency of ArF light. The acid-decomposable resin (A) can be synthesized by a conventional method (for example, radical polymerization). For example, the general synthesis method is to add the monomers at one time or into the reaction container during the reaction, and dissolve the substance in the reaction solvent as required (such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, etc.). Ethers or ketones such as methyl ethyl ketone, methyl isobutyl ketone, etc., ester solvents such as ethyl acetate, and solvents such as the following propylene glycol monomethyl ether acetate) to dissolve the composition of the present invention After forming a homogeneous phase, heat it in an inert gas atmosphere such as nitrogen or argon as needed, and start polymerization using a commercially available free radical polymerization initiator (azo-based initiator, peroxide, etc.) . If necessary, additional initiators or batches may be added. After completion of the reaction, the polymer may be recovered by recovering powder or solids by putting it into the solvent. The reaction concentration is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and more preferably 50 ° C to 100 ° C. The above-mentioned repeating structural units may be used singly or in combination. In the present invention, one kind of resin may be used, or several kinds of resins may be used. When the weight-average molecular weight of the acid-decomposable resin (A) is converted to polystyrene by GPC. Method, it is preferably 1,000 to 200,000, and more preferably 3,000 to 20,000. By setting the weight-average molecular weight to be 10,000 or more, heat resistance and dry etching resistance can be improved from -35 to 200534042. In addition, by setting the weight-average molecular weight to 200,000 or less, it is possible to improve developability, reduce viscosity, and improve film formation. Sex. The molecular weight distribution (Mw / Mn, also referred to as the degree of dispersion) is usually from 1 to 5, preferably from 1 to 4, and most preferably from 1 to 3. In terms of resolution, photoresist shape, sidewall of photoresist pattern, roughness, etc., the molecular weight distribution is preferably 5 or less. In the positive-type photoresist composition of the present invention, the compounding amount of the acid-decomposable resin is preferably 40 to 99.99% by mass, and more preferably 50 to 99.97% by mass, based on the total solid content of the photoresist. [2] (B) Compounds that generate acid by irradiation with active light or radiation Related to the positive-type photoresist composition for liquid immersion exposure of the present invention, compounds that generate acid by irradiation with active light or radiation (hereinafter referred to as " The acid generator ") is described below. The acid generator used in the present invention can be selected from compounds generally used as acid generators. In other words, it can be appropriately selected from the group consisting of photo-cationic polymerization photoinitiator, photo-radical polymerization photo-initiator, pigment-type light decolorizer, photochromic agent, or microphotoresist. Radiation exposure produces conventional compounds of acids and mixtures thereof. For example, there are diazo key salts, scale salts, yellow salts, iodine key salts, ammonium sulfonate, oxime sulfonate, diazobisamidine, diamidine, and o-nitrobenzyl sulfonate. In addition, the compounds that generate an acid group or a compound introduced into a polymer main chain or a side chain by irradiation with active light or radiation can be used, for example, -36-200534042, US Patent No. 3,849,137, German Patent No. 3 9 1 4407, Japanese Patent Application No. 6 3-2665 No. 3, Japanese Patent Application No. 5 5-1 64 824, Japanese Patent Application No. 62-69263, Japanese Patent Application No. 63- 1 4603, Japanese Patent Application No. 6 Compounds described in 63-1 63452, JP 62-153853, and JP 63-146029. In addition, compounds that generate an acid by light as described in U.S. Patent No. 3,779,77 8 and European Patent No. 126,712 can also be used. Preferred compounds among the acid generators include compounds represented by the following general formulae (ZI), (ZII), and (ZIII). ^ 201R202_ Yu ten X- ^ 203 Zl R204 a t " R20S χ- Z (l

OMSno I / OMSHO tζιπ In the general formula (ZI), R2 () 1, R202, and R20 3 each represent an independent organic group. X is a non-nucleating anion. In general, the carbon number of the organic group of r2 () 3 is 1 to 30, preferably 1 to 20. And 'R2. At least two of R2Q3 may be bonded to form a ring structure, and the ring may also contain an oxygen atom, a sulfur atom, an ester bond, an amidine bond, and a carbonyl group. R2 (n ~ R203) formed by at least two bonds, for example, alkylene (such as butylene, pentapentyl). R2 (H, R202 and r2 () 3 specific organic groups For example, the groups corresponding to the following compounds (Zl-1), (Z1-2), and (Z1-3) are as follows. -37- 200534042 Furthermore, the compound may have a structure represented by several general formulas (ZI). For example, a compound having a structure in which at least one compound represented by general formula (ZI) R2., ~ R2 () 3 is bonded to another R2 (H ~ R203) of at least one compound represented by general formula (ZI). More preferred (ZI) components are, for example, compounds (Z1-1), (Z1-2), and (Z1-3) described below. The compound (Z1-1) is at least one of the above-mentioned general formula (ZI) 2 R2 ( ) 1 ~ R203 is an aryl salt of an aryl group, that is, a compound and compound using the aryl salt as a cation. All the aryl salt compounds may be R2 () 1 ~ R203 as an aryl group, or Part of R2 (H ~ R203 is an aryl group, and the rest are an alkyl group or a cycloalkyl group. Examples of the aryl sulfonium salt compound include a triaryl salt, a diaryl alkyl salt, an aryl dialkyl salt, Diarylcycloalkyl salt Compounds, aryl bicycloalkyl salt compounds, etc. The aryl group of the aryl salt compounds is preferably phenyl or naphthyl, and the more preferred is φphenyl. When the aryl salt compounds have more than two aryl groups , 2 or more aryl groups may be the same or different. The aryl salt compound may have an alkyl group as required, and a linear or branched alkyl group having 1 to 15 carbon atoms is preferred, such as methyl, ethyl , Propyl, n-butyl, 2-butyl, 3-butyl, etc. The aryl sulfonium salt compound has a cycloalkyl group as required, and a cycloalkyl group having 3 to 15 carbon atoms is preferred, For example, cyclopropyl, cyclobutyl, cyclohexyl, etc. R2 (aryl group, alkyl group, cycloalkyl group from h to R2Q3, may have alkyl group (for example, -38- 200534042 carbon number 1 to 15), cyclohexyl group (For example, carbon number 3 to 15), aryl (for example, carbon number 6 to 14), alkoxy (for example, carbon number 1 to 15), halogen atom, hydroxyl group, phenylthio group, etc. as a substituent. Preferred substitution The radicals are linear or branched alkyl radicals having 1 to 12 carbon atoms, cycloalkyl radicals having 3 to 12 carbon atoms, and alkoxy radicals having 1 to 12 carbon atoms. The most preferred are alkyl radicals having 1 to 4 carbon atoms. Alkoxy group having 1 to 4 carbon atoms. Substituents may be Substitute any one of R2i) 1 ~ R203, or all of them may be substituted. In addition, when R2 (n ~ R203 is an aryl group, it is preferable to substitute a substituent at the P-position of the aryl group. The non-nucleating anion of X 'includes, for example, a sulfonic acid anion, a carboxylic acid anion, a sulfofluorenimide anion, a bis (alkylsulfonyl) imide anion, and a (alkylsulfonyl) methyl group. Base anions, etc. Non-nucleating anions are anions that have extremely low ability to cause a nuclear-seeking reaction. 'Anions that can be decomposed over time by nuclear-seeking reactions within the molecule. This can improve the stability of the photoresist over time. Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic anion φ ion, and a camphor sulfonic acid anion. Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkylcarboxylic acid anion. Examples of the aliphatic group of the aliphatic sulfonic acid anion include an alkyl group having 1 to 30 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and 2-butyl groups. , Pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, cetyl, heptadecyl Group, octadecyl group, nonadecyl group, eicosyl group, -39-200534042, and cycloalkyl group having 3 to 30 carbon atoms. Specific examples include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, Jiangyin Yuanji, Borneol, etc. The aromatic group of the aromatic sulfonic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl, tolyl, and naphthyl. The alkyl group, cycloalkyl group, and aryl group of the aliphatic sulfonic acid anion and aromatic sulfonic acid anion may have a substituent. Examples of the substituent include a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably a carbon number of 1 to 5), and a cycloalkane. (Preferably 3 to 15 carbons), aryl (preferably 6 to 14 carbons), alkoxycarbonyl (preferably 2 to 7 carbons), fluorenyl (preferable is Carbon number 2 to 12), alkoxycarbonyloxy group (preferably, carbon number 2 to 7), alkylthio group (preferably, carbon number 1 to 15), and the like. The aryl group and the ring structure possessed by each group may be, for example, an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent. The aliphatic group of the aliphatic carboxylic acid anion may be the same as the aliphatic group of the aliphatic sulfonic acid anion, for example. The aromatic group of the aromatic carboxylic acid anion may be the same as the aromatic group of the aromatic sulfonic acid anion, for example. The aralkyl group of the aralkylcarboxylic acid anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, and naphthylethyl. The aliphatic carboxylic acid anion, aromatic carboxylic acid anion, and aralkyl carboxylic acid anion may have an # group, and the substituent may be the same as the aliphatic sulfonic acid anion. Halogen atom, academic group, cyclic academic group, academic group, sulfanyl group, etc. -40 · 200534042 sulfofluorenimine anion such as saccharin anion. The alkyl group of the bis (alkylsulfonyl) sulfonium imide anion and the (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, Isopropyl, n-butyl, isobutyl, 2 · butyl, pentyl, neopentyl and the like. These alkyl groups may have a substituent, such as a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, and an alkyl group substituted with a halogen atom is preferred. Other non-nucleating anions include phosphorus fluoride, boron fluoride, antimony fluoride, and the like. The non-nucleating anion of X · is an aliphatic sulfonic acid anion substituted with a fluorine atom at the α position of the sulfonic acid, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and a disubstituted alkyl group with a fluorine atom. The (alkylsulfonyl) sulfonium imide anion and the para (alkylsulfonyl) methylation anion in which the alkyl group is substituted with a fluorine atom are preferred. Non-nucleating anions are more preferably perfluorinated aliphatic sulfonic acid anions having 4 to 8 carbon atoms, and aromatic sulfonic acid anions having fluorine atoms, and nonfluorinated butanesulfonic acid anion and perfluorinated octanesulfonic acid are preferred. Anions, pentafluorobenzenesulfonic acid anions, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anions are the best. Next, the related compound (Z1-2) will be described. The compound (Z1-2) is a compound in the general formula (Z1) when each of 2.1 to 112.3 represents an independent organic group containing no aromatic ring. Among them, the aromatic ring also includes a hetero atom-containing aromatic ring. R2 (M ~ R203, organic group without aromatic ring, generally 1 ~ 30 carbon atoms, preferably 1 ~ 20. -41-200534042 R201 ~ R203 are each independent JjL fluorenyl group, ring Academic, square, and ethyl groups are preferred. The more preferred are linear, branched, cyclic 2-carbonylalkyl, and alkoxycarbonylmethyl. The most preferred are linear and branched 2-carbonylalkyl. R2 (n ~ R203 may be straight or branched, preferably a straight or branched alkyl having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butane Group, pentyl, etc. More preferably, the alkyl group is a 2-linear or branched carbonylalkyl group or an alkoxycarbonylmethyl group. A cycloalkyl group of R2 (n ~ R203) is a cycloalkane having 3 to 10 carbon atoms. Preferably, the alkyl group is, for example, cyclopentyl, cyclohexyl, norbornyl, etc. The cycloalkyl group is more preferably a 2-carbonylcycloalkyl group. The 2-carbonylalkyl group may be straight chain, branched chain, or cyclic. The above-mentioned alkyl group and cycloalkyl group have a group of> C = 0. The alkoxy group of the alkoxycarbonylmethyl group is preferably an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, Propyl, butyl, pentyl). R20 1 ~ R20 3 can also be halogen atom, oxygen (such as carbon number 1) ~ 5), substituted with a group, cyano, and nitro. R2 (M ~ R203 may be bonded to form a ring structure with two bonds, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amidine bond, and a carbonyl group. R2 (M ~ R203 is formed by two bonded groups such as butylene (eg, butylene, butyl). Compound (Z1-3) is represented by the following general formula (Z1-3) The compound is a compound having a benzamidine sulfonium salt structure. -42-200534042

(Z1-3) R !. ~ R5. Each represents an independent hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom. φ and R represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

Rx and Ry each represent an independent alkyl group, cycloalkyl group, aryl group or vinyl group.

Ri. ~ R5. Any two or more of them, and Rx and Ry are each bonded to form a ring structure, and the ring structure may also include an oxygen atom, a sulfur atom, an ester bond, and a amide bond.

Zc_ represents a non-nucleating anion, for example, the same as the non-nucleating anion of X- in the general formula (ZI). ~ R7. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, straight or branched propyl, straight or branched butyl, and straight or branched chain. Amyl and others.

Ru ~ R7. The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopentyl and cyclohexyl.

Rlc ~ R5. The alkoxy group may be linear, branched, or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms (for example, methoxy, Ethoxy, straight or branched propoxy, straight or branched butoxy, straight or branched pentoxy), cyclic alkoxy having 3 to 8 carbon atoms (such as cyclopentyloxy, Cyclohexyloxy). -43- 200534042 The better one is Ri. Any one of ~ Rk is a linear or branched fluorenyl group, a cycloalkyl group, or a linear, branched, or cyclic alkoxy group, and more preferably R i ε to R 5. The sum of carbon numbers is 2 to 15. This can further improve the solubility of the solvent, and can suppress the occurrence of particles during storage. And Ry's alkyl and cycloalkyl are, for example, Ri. ~ R7. In the case where the alkyl group and the cycloalkyl group are the same, 2-carbonylalkyl, 2-carbonylcycloalkyl, and alkoxycarbonylmethyl are more preferred. Examples of 2-carbonylalkyl and 2-carbonylcycloalkyl are R !. An alkyl group and a cycloalkyl group at the 2-position have a group of > C = 0. The alkoxy group of the alkoxycarbonylmethyl group is, for example, the same as the alkoxy group of ~.

Examples of the group formed by bonding Rx and Ry include butyl and pentyl.

Rx and Ry are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and most preferably 8 or more alkyl groups. In the general formulae (ZII) and (ZIII), each of R2m to R2Q7 represents an independent aryl group, a group, or a ring group. R2 04 ~ R2. The aryl group of 7 is preferably a phenyl group and a Chai group, and more preferably a phenyl group. R2 (M ~ R2 0 7 alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, etc. R2 04 ~ R2. The cycloalkyl group of 7 is preferably a cycloalkyl group having 3 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, norbornyl, etc. Substituents which R2 04 to R2 0 may have, such as alkyl (such as Carbon number 1 ~ 15), cycloalkyl group (such as carbon number 3 ~ 15), aryl group (such as carbon number 6 ~ 15), alkoxy group (such as carbon-44-200534042 number 1 ~ 15), halogen atom, hydroxyl group , Phenethyl, etc. X- represents a non-nucleating anion, which is the same as the non-nucleating anion of X- in the general formula (ZI). Preferred compounds among the acid generators include the following: Compounds represented by the formulae (ZIV), (ZV), and (ZVI).

In the general formulae (ZIV) to (ZVI), An and Ar4 each represent an independent aryl group. R206, R2Q7, and R208 are the basic, ring, or aryl groups.These can be compared with the groups, ring, or aryl groups of R204 to R207. A means alkylene, alkenylene, or alkylene. Aryl. Among the acid generators, compounds represented by the general formulae (ZI) to (ZIII) are more preferred. Among the compounds which generate an acid by irradiation with active light or radiation, it is more preferable as described below. -45- 200534042

〇3Γ

(〇fs + c 彳 as ㈣ 3 (〇, zero 〇.-㈣ (ζ7) ㈣

(卿 〇4pftS〇x * ύ m

ο Money ’m + G4F9SO 疒

-46- 200534042

CF3S03, (free) ρά ~ 一 I o 〇4 ^ 5〇3 " * (z22) CF ^ SOg 'C4F9SO3- (z25 > < 3 丄 C3F17SO3-㈣C〇Ft7S〇r ^ (z26) 〇

NO'S-CFa ^ -〇-S-Cf3 (BcJn N 0-S-CFa (Z27) (Z29)

QN2〇 s-c-s o 0 (z30)

(Z31)

〇N3〇 I -S-C—S-ί— H 44 Io o 1

Mea

n.〇- | -CF3 HsCH2CH2C- | 〇, Ni ^ OS-CH2CH2CH3 (z34)

(zS3) O

CFsSOa- (z35) S03, ㈣a ^ S〇3- (z37) sPl 5 (z38) 6sSs〇3-

, SOi: f MeO S + 〇4; FdS〇3- OBu

(z39) 0

Gi | FgS〇3ta (z4D) (241) C / jF ^ SOa ^ (柳

0-(XsO ㈣) G4FgS〇3 ~ -47- 200534042

xyVs0

Another sO C4F9SO3- (z46) fS ^ C4F0SO3- ό • (z47) (^ 45)

〇 eHl7 0 G4F3S03- (z49) 0 ^: G4H9 C4F9S03- (zsa) C4F9S03- (z63)

F + F FI ^ IF FII-F FI ^ IF): s + ϊ Z5

F F U51)

0 and S〇3 一 (254) 〇 C12Hzs 〇 ^ δ, 12Η25 O ^ F ^ SOg- (¢ 52)

2h cl a s +

Γ-F p J-F 057) PIHF Jvz F-F

Vo

F5F5 C2C2 On household, 5HO l / N, ll o; 09) s 3 S acid generator can be used alone or in combination of two or more. The content of the acid generator in the positive type photoresist composition for liquid immersion exposure is based on the entire solid content of the photoresist composition as a reference, preferably from 0.1 to 20% by mass, and more preferably from -48 to 200534042, which is 0.5 to 10% by mass, and the best is 1 to 7% by mass. [3] (C) Increasing the solubility in alkali developing solution by decomposition by acid action, the compound with a molecular weight of less than 3,000 preventing the dissolution prevents the positive photoresist composition for liquid immersion exposure of the present invention to contain decomposition by acid action To increase the solubility in an alkali imaging solution, a dissolution preventing compound having a molecular weight of 3,000 or less (hereinafter referred to as a "dissolution preventing compound") is preferred. When the dissolution preventing compound does not lower the permeability below 220 nm, the acid-decomposable group-containing alicyclic group containing an acid-decomposable group-containing alkyd derivative as described in Proceeding of SPIE, 2724,355 (1 996) Or an aliphatic compound is preferred. The acid-decomposable group and the alicyclic structure are the same as those described for the acid-decomposable resin (A), for example. The molecular weight of the dissolution preventing compound of the present invention is 3,000 or less, preferably 300 to 3000, and more preferably 500 to 2500. The addition amount of the dissolution preventing compound is preferably 1 to 30% by mass, and more preferably 2 to ^ 20% by mass for all solid components of the positive type photoresist composition for liquid immersion exposure. The following are specific examples of the dissolution preventing compounds, but are not limited thereto. -49- 200534042

. People

OH ^^-COO ^ t-Bu ^^-COO- ^ Bu -50- 200534042 [4] (D) A basic compound is used in the positive-type photoresist composition for liquid immersion exposure of the present invention to further contain alkaline Compounds are preferred. As the basic compound, for example, a nitrogen-containing basic compound, a basic ammonium salt, a basic salt, or a basic iodonium salt can be used as long as it does not cause sublimation or decrease in photoresistance. The basic compound is a component having a function of suppressing the diffusion of an acid generated from the acid generator by photoexposure in the photoresist film, and suppressing a non-desired chemical reaction in a non-exposed range. By blending the basic compound, it is possible to suppress the diffusion of the acid generated from the acid generator by exposure in the photoresist film, to improve the storage stability of the obtained positive photoresist composition for liquid immersion exposure, and to improve the light. The resolution of the resist can suppress the change in the line width of the photoresist pattern caused by the change in the placement time (PED) from exposure to development processing, and can obtain a composition with excellent process safety. Examples of nitrogen-containing basic compounds include primary, secondary, and tertiary aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, and nitrogen-containing compounds having a hydroxyl group. Compounds, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amidine derivatives, amidine derivatives, nitrogen-containing compounds having a cyano group, and the like. Examples of aliphatic amines are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, 2-butylamine, 3-butylamine, pentylamine, 3-pentylamine, and cyclopentylamine , Hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylpentylamine, dimethylamine, diamine Ethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, -51-200534042 di-n-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, Diheptylamine, dioctylamine, dinonylamine, didecylamine, di-dodecylamine, di-hexadecylamine, N, N-dimethylmethyldiamine, N, N-dimethylethylenediamine Amine, N, N-dimethyltetraethylpentylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-isobutylamine, tri-n-butylamine Amylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tri-dodecylamine, trihexadecylamine, N, N , N ,, N, -tetramethylmethyldiamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N, -tetramethyl Extending ethyl pentylamine ,, dimethyl amine, methyl ethyl propyl amine, benzylamine, phenethylamine, benzyl dimethylamine and the like. Aromatic amines and heterocyclic amines, such as aniline derivatives (such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methyl Aniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-bis Nitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (P · tolyl) amine, methyldiphenylamine, Triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (such as pyrrole, 2Η-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (such as oxazole, isoxazole, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4-methylimidazole, 4- Methyl-2-phenylimidazole, etc.), pyrazole derivatives, brazil hydrocarbon derivatives, pyrroline derivatives (such as pyrroline, 2-methyl-1 -pyrroline, etc.), pyrrolidine derivatives (such as pyrrolidine , N-methylpyrrolidine, pyrroline, N-methyl Pyrrolidone, etc.), -52- 200534042 imidazoline derivatives, imidazolium derivatives, pyrazine derivatives (such as pyrazine, methylpyrazine, propylpyrazine, butylpyrazine, 4-(1-butylpentane) Base) Pycnogenol, dimethylpyridine trap, trimethylpyridine trap, triethylpyridine, phenylpyridine trap, 3-methyl-2-phenylpyridine trap, 4-3rd-butylpyridine trap, Diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinylpyridine, 1- Methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridyl derivatives, pyrimidine derivatives, pyridyl derivatives, pyrazolines Derivatives, pyrazolidine derivatives, piperidine derivatives, piperidine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1 H-indole derivatives, indolin derivatives, quinine Phthaloline derivatives (such as quinoline, 3-quinolinecarbonyltolyl, etc.), isoquinoline derivatives, perylene derivatives, quinazoline derivatives, quinoxaline derivatives, phthaloline derivatives, purine derivatives, Pteridine derivatives, carbazole derivatives Compounds, phenanthridine derivatives, acridine derivatives, phenoxine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives Substance 'uridine derivatives and so on. Nitrogen-containing compounds having a carboxyl group, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (such as nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, groups Amino acid, isoleucine, glycidyl leucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyran-2-carboxylic acid, methylamine Oxyalanine) and so on. Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridinium, and the like. -53- 200534042 The nitrogen-containing compound having a radical is, for example, 2-hydroxypyridine, aminocresol, 2,4-quinolinediazole, 3-indole hydride, monoethanolamine, diethanolamine, diethanolamine, N- Ethyl monoethanolamine, n, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino · 1-propanol, 4-amine 1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1-(2-hydroxyethyl) piperidine, 1-[2-(2-hydroxy Ethoxy) ethyl] piperazine, pyrazine ethanol, 1-(2-hydroxyethyl) pyrrolidine, 1 _ (2 _hydroxyethyl) _ 2 · pyrrolidone, 3 -piperazyl-1,2 -Propylene glycol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxyjulonidin, 3-raptorinol, 3-tropinol, 1-methyl-2 -pyrrolidine ethanol, 1-nitrogen Heteropropane ethanol, > 1- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamine, and the like. The amidine derivatives are, for example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide Amine, propylamine, benzopyramine and the like. The fluorenimine derivatives include, for example, phthalimide, squalene sulfonimide, and maleimide. Specific examples of the nitrogen-containing compound having a cyano group include 3- (diethylamino) propionitrile, N, N-bis (2-hydroxyethyl) -3-aminopropionitrile, and N, N-bis (2- Acetyloxyethyl) -3-aminopropionitrile, N, N-bis (2-methoxymethylethyl) -3 · aminopropionitrile, N, N-bis (2-methoxyethyl) ) -3-aminopropionitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionitrile, N- (2-cyanoethyl) · N- (2-methoxyethyl) -3-aminopropanoic acid methyl ester, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropanoic acid methyl ester, N -(2-Ethyloxyethyl) -N- (2-cyanoethyl) -3 · amine-54- 200534042 methyl propionate, N- (2-cyanoethyl) -N-ethyl 3-aminopropionitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionitrile, N- (2-ethoxyethyl)- N- (2-cyanoethyl) -3-aminopropionitrile, N- (2-cyanoethyl) -N- (2-methylaminoethyl) -3 · aminopropionitrile, N -(2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionitrile, N- (2-cyanoethyl) -N- [2- (methoxymethyl (Oxy) ethyl] -3-aminopropionitrile, N- (2-cyanoethyl) -N- (3-hydroxy-butylpropyl) -3-aminopropyl Nitrile, N- (3-Ethoxymethyl-1-propyl) -N- (2-cyanoethyl) -3-aminopropionitrile, N- (2-cyanoethyl) -N- ( 3-methoxymethyl-1-propyl) -3-aminopropionitrile, N- (2-cyanoethyl) -N-tetrahydrofuryl-3-aminopropionitrile, N, N-bis (2 -Cyanoethyl) -3-aminopropionitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetamidoethoxyethyl) Group) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropanoic acid methyl ester, N-cyanomethyl -N- (2-hydroxyethyl) -3-aminopropanoic acid methyl ester, N- (2-ethoxyethyl) -N-cyanomethyl-3-aminopropionic acid methyl ester, N -Cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-ethoxymethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl -N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl- N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, N- (Cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-ethoxymethyl-1-propyl) -N- (cyanomethyl) aminoacetonitrile , N-cyanomethyl-N- (3-methylphenoxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropionitrile, 1 -Piperazine propionitrile, 4-morpholine propionitrile, 1-pyrrolidine acetonitrile, -55- 200534042 bupicol acetonitrile, 4-morpholine acetonitrile, 3-diethylamino propionate cyanomethyl ester, n, N-bis (2-hydroxyethyl) -3-aminopropanoic acid cyanomethyl ester, n, N-bis (2-ethylacetoxyethyl) -3-aminopropanoic acid cyanomethyl ester, n , N-Bis (2-methoxyethyl) · 3-aminopropanoic acid cyanomethyl ester, N, N-bis (2-methoxyethyl) -3-aminopropanoic acid cyanomethyl ester Ester, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropanoic acid cyanomethyl ester, 3 · diethylaminopropionic acid (2-cyanoethyl) , N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-ethoxyethyl) -3-aminopropyl Acid (2-cyanoethyl), N, N · bis (2-methylaminoethyl) -3-aminopropane® acid (2-cyanoethyl), N. N-bis (2-methoxyethyl) _3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3_amine Propanoic acid (2-cyanoethyl ester), 1-pyrrolidine propanoic acid cyanomethyl ester, 1. piperidine propanoic acid cyanomethyl ester, 4-morpholine propanoic acid cyanomethyl ester, 1-pyrrolidine propane Acid (2-cyanoethyl), 1-piperapropionic acid (2. cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl). Nitrogen-containing basic compounds with 1,5-diazobicyclo [4. 3. 0] -5-nonene, 1,8-diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diazobicyclo [2. 2. 2] Octane, φ "dimethylaminopyridine, 1-naphthylamine, pyridine, hexamethylenetetramine, imidazole, hydroxypyridine, pyridine, aniline, hydroxyalkylaniline, 4 , 4'-Diaminodiphenyl ether, pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridine P-toluenesulfonate, tetramethylammonium P-toluenesulfonate, tetrabutyl Ammonium laurate, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, triisooctylamine, ginsyl (ethylhexyl) amine, tridecylamine, tri-dodecylamine, tri-n-propylamine, Tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine 'methyldicyclohexylamine, ethylenediamine , -56 · 200534042 N, N, N ,, N, -tetramethylethylenediamine, tetramethyldiamine, hexamethyldiamine, 4,4, diaminodiphenylmethane, 4,4, -diamine Diphenyl ether, 4,4, diaminobenzophenone, 4,4, -diaminodiphenylamine, 2,2-bis (4-aminophenyl) both houses, 2- (3- Aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxy Group) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis [1- (4-aminophenyl) -bumethylethyl] benzene, bis (2 · dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, N, N, N ', N'-(2-Ethylpropyl) ethylenediamine, Tricyclohexylamine and other Φ tri (cyclo) alkylamines, aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, Aromatic amines such as 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,6-diisopropylaniline, polyethylene diamine, polyallylamine, 2-dimethylaminoethylpropene Polymers of stilbene amine, Nt-butoxyl-di-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, N + butoxy Carbonylcyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl · N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl · 1-adamantylamine, N, N-di + butoxycarbonyl-N-methyl-amantadine, Nt-butoxycarbonyl · 4,4'-diaminophenylmethane, Ν, Ν '-Di-t-butoxycarbonylhexamethylene , N, N, N ', N'-tetra-t-butoxycarbonylhexamethyldiamine, N, N'-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N '-Di-butoxycarbonyl-1,8-diaminooctane, N, N'-di-tl, 9-diaminononane, N, N'-di-small-butoxycarbonyl-1, 10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t-butoxycarbonyl-4,4 '-Diaminodiphenylmethane, Nt-butoxycarbonyl benzimidazole, Nt-butoxy-57- 200534042 carbonyl-2-methylbenzimidazole, N-t-butoxycarbonyl-2- Phenylbenzimidazole, formamidine, N-methylformamide, ν, N-dimethylformamide, acetamide, Ν-methylacetamide, Ν, Ν-dimethylacetamide , Propylamidine, benzopyramine, pyrrolidone, N-methylpyrrolidone, urea, methylurea, dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetram Methylurea, 1,3-diphenylurea, tri-n-butylurea sulfide, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzene Imidazoles such as benzimidazole, pyridine, 2-methylpyridine, 4-methylpyridine 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylIpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, ammonium nicotinate, Β Quinoline, 4-quinylquinoline, 8-quinolinyl oxide, 0-Ya quinidine, etc., B-type, pulse coax, 1- (2-hydroxyethyl) pipe traps, pipe traps, etc. Pyrazole, pyridine, quinoxaline, purine, pyrrolidine, pyridine, 3-pyrrolidinyl-1,2-propanediol, morpholine, 4-methylmorpholin, 1,4 · dimethylpyridine, etc. Better. Among these, 1,5-diazobicyclo [4. 3. 0] -5-nonene, 1,8-diazobicyclo [5. 4. 0] -7-undecene, 1,4-diazobicyclo [2. 2. 2] octane, | 4-dimethylaminopyridine, 1-naphthylamine, pyridine, 4-hydroxypyridine, 2,2,6,6-tetramethyl · 4-hydroxypyridine, hexamethylenetetramine , Imidazoles, hydroxypyridines, orbipyridines, 4,4'-diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, hydrazone-η-octylamine, ginsyl (ethylhexyl) Nitrogen-containing basic compounds such as amine, tris-tridecylamine, N, N-di-hydroxyethylaniline, N-hydroxyethyl · N · ethylaniline are more preferred. In the positive type photoresist composition for liquid immersion exposure of the present invention, a basic ammonium salt may be used as a basic compound. Specific examples of the basic ammonium salt are not limited to the compounds shown below. -58- 200534042 Specific examples are ammonium hydroxide, ammonium trifluoride, ammonium pentafluoride, ammonium heptafluoride, ammonium nonafluoride, ammonium unfluoride, ammonium trifluoride, ammonium pentafluoride, methyl Ammonium carboxylic acid, ammonium ethylcarboxylic acid, ammonium propylcarboxylic acid, ammonium butylcarboxylic acid, ammonium pentylcarboxylic acid, ammonium hexylcarboxylic acid, ammonium octylcarboxylic acid, nonylcarboxylic acid Ammonium salt, ammonium decylcarboxylic acid, ammonium undecylcarboxylic acid, ammonium salt of dodecylcarboxylic acid, ammonium salt of tridecylcarboxylic acid, ammonium salt of tetradecylcarboxylic acid, pentadecyl Ammonium carboxylate, ammonium hexadecylcarboxylate, ammonium hexadecylcarboxylate, ammonium octadecylcarboxylate, and the like. • Specific examples of the above ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentyl ammonium hydroxide, tetrahexyl iron hydroxide, Heptyl dihydroxide, methyltrioctyl ammonium hydroxide, tetraoctyl ammonium hydroxide, didecyl dimethyl ammonium hydroxide, decyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, Dodecylethyldimethylammonium hydroxide, di-dodecyldimethylammonium hydroxide, tri-dodecylmethylammonium hydroxide, myristylmethylammonium hydroxide, dimethyl Di-tetradecyl alkyl ammonium hydroxide, cetyl trimethyl ammonium hydroxide, octadecyl trimethyl ammonium hydroxide, dimethyl di-octadecyl ammonium hydroxide, tetradecyl Octaalkylammonium hydroxide, diallyldimethylammonium hydroxide, (2-chloroethyl) -trimethylammonium hydroxide, (2-bromoethyl) trimethylammonium hydroxide, ( 3-bromopropyl) trimethylammonium hydroxide, (3-bromopropyl) triethylammonium hydroxide, epoxypropyltrimethylammonium hydroxide, choline hydroxide, (R)-( +)-(3-Chloro-2-hydroxyl Group) trimethylammonium hydroxide, (S)-(-)-(3-chloro-2-hydroxypropyl) -trimethylammonium hydroxide, (3-chloro-2-hydroxypropyl)- Trimethylammonium hydroxide, (2-amino-59-200534042 ethyl) -trimethylammonium hydroxide, hexamethylammonium hydroxide, decamethylammonium hydroxide, 1-azokey salt propeller alkane hydroxide Alkali compounds, petroleum hydroxide, 2-chloro-1,3-dimethyl-2-imidazolium hydroxide salt, and 3-ethyl-2-methyl-thiazole hydroxide salt can be used alone or in combination of two or more. It is preferred to use two or more types. The amount of the basic compound used is based on the solid content of the positive photoresist composition for liquid immersion exposure, and usually 0. 001 to 10% by mass, preferably 0.1%. 01 • ~ 5% by mass as the total amount. [5] (E) Surfactant The positive photoresist composition for liquid immersion exposure of the present invention preferably contains (E) a surfactant, and contains a fluorine-based and / or silicon-based surfactant (fluorine Any one of the surfactants, silicon surfactants, and surfactants having both a fluorine atom and a silicon atom), or two or more thereof is preferred. The positive-type photoresist composition for liquid immersion exposure of the present invention, when containing the above (E) surfactant, is used at an exposure light source of less than 250 nm, especially less than 220 nm. Sensitivity and resolution, a photoresist pattern with few adhesion and development defects can be obtained. Fluorine-based and silicon-based surfactants include, for example, Japanese Patent Laid-Open No. 6 2 _ 3 6 6 6 3, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 6 1-226745, and Japanese Patent Laid-Open No. 62- 1 Gazette No. 70950, Gazette No. 63-34540, Gazette No. 7-230 1 65, Gazette No. 8-62834, Gazette No. 9-5 4432, Gazette No. 9-5988, Gazette Publication No. 2002-277862, -60-200534042 _ US Patent No. 5405720, same as No. 5360692, same with No. 5529881, same with No. 5296330, no. 5436098, no. 5 5 7 6 1 No. 43, no. 5 The surfactants described in Specification 2945 1 and 5 8 2445 are the same as those described in the Specification No. 1 and the following commercially available surfactants. Commercially available surfactants include, for example, Yabundo (Transliteration) EF301, EF3 03 (produced by Shin Akita Kasei Co., Ltd.), Brolaton (Transliteration) FC430, 431 (Sumitomo Sliem (Transliteration) ( System), Mekafak (translated ^ sound) F17, F173, F176, F189, R0 8 (Da Nihon Ink Chemical Industry Co., Ltd.), Sablon (transliterated) S-382, SC101, 102, 103 , 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Dun Long Yiluolu (transliteration) s-366 (don Long Yi (transliteration) chemical (stock)) and other fluorine-based surfactants or silicon-based interface Active agent. In addition, a polysiloxane polymer KP_341 (made by Shin-Etsu Chemical Industry Co., Ltd.) may be used as the silicon-based surfactant. In addition, in addition to those shown above, a fluorine-based aliphatic compound prepared by adjusting a polymerization φ reaction method (also referred to as a telomerization method) or an oligomerization method (also referred to as an oligomerization method) may be used. A surfactant derived from a polymer having a fluorine-based aliphatic group is used as the surfactant. The fluorine-based aliphatic compound can be synthesized by the method described in Japanese Patent Application Laid-Open No. 200 2-9099. A polymer having a fluorine-based aliphatic group is preferably a copolymer of a monomer having a fluorine-based aliphatic group and (polyepoxyalkyl) acrylate and / or (polyepoxyalkyl) methacrylate, Can be irregularly distributed or block copolymerized. In addition, poly (alkylene oxide) includes, for example, polyethylene oxide, polypropylene oxide, polycyclo-61-200534042 oxetane, and the like, and poly (ethylene oxide, polypropylene oxide, and ring). Units of oxyethylene (block block), or poly (block bonds of ethylene oxide and propylene oxide), and other units with different chain lengths within the same chain length. In addition, a copolymer of a monomer having a fluorine-based aliphatic group and (poly (alkylene oxide)) acrylate (or methacrylate) may be a binary copolymer or two or more kinds of fluorine-containing copolymers. A monomer based on an aliphatic group or a ternary or higher copolymer copolymerized with two or more different (poly (alkylene oxide)) acrylates (or methacrylates) at the same time. For example, commercially available surfactants include Merck F178, F-470, F-47 3, F-47 5, F-47 6, F-47 2 (made by Dainippon Ink Chemical Industry Co., Ltd.). In addition, for example, a copolymer of an acrylate (or methacrylate) having a CeFu group and (poly (alkylene oxide)) acrylate (or a methacrylate), an acrylate (methacrylate) having a C6F13 group ) And (poly (ethylene oxide)) acrylate (or methacrylate) and (poly (propylene oxide) acrylate (or methacrylate)) copolymers, acrylate (C8F17) Copolymer of acrylic acid ester) and (poly (alkylene oxide)) acrylic acid ester (or methacrylic acid ester), acrylic acid ester (methacrylic acid ester) and (poly (ethylene oxide)) acrylic acid having C8F17 group Copolymers of esters (or methacrylates) and (poly (propylene oxide) acrylates (or methacrylates)). Moreover, the present invention can also use a surfactant other than a fluorine-based and / or silicon-based surfactant. Specifically, for example, polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide cetyl ether, polyethylene oxide oleyl ether and the like Ethylene oxide octyl phenol ether, polyethylene oxide-62-200534042 Nonyl phenol ether and other polyethylene oxide alkyl allyl ethers, polyethylene oxide · polypropylene oxide block copolymer Class, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbose Sorbitan anhydride fatty acid esters such as alkyd tristearate, polyethylene oxide sorbitan monolaurate, polyethylene oxide sorbitan monopalmitate, polyethylene oxide Polysorbate fatty acid such as sorbitan monostearate, polyethylene oxide sorbitan trioleate, polyethylene sorbitan tristearate, etc. Nonionic surfactants such as esters. These surfactants can be used singly or in combination. (E) The amount of the surfactant used is 0. for the total amount of the positive photoresist composition for liquid immersion exposure (except for the solvent). 0001 ~ 2 mass% is better, and more preferably 0. 0 0 1 to 1% by mass. [6] (F) Organic solvent The positive-type photoresist composition for liquid immersion exposure of the present invention can be used by dissolving the above components in a predetermined organic solvent. The organic solvents used include, for example, dichloroethane, dicyclohexanone, cyclopentanone, 2-heptanone, r-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methoxy Methyl propionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, n, n-dimethylformamide, dimethylmethylene, N-methylpyrrolidone , Methoxybutanol, tetrahydrofuran • 63-200534042 In the present invention, a solvent having a hydroxyl group in the structure and a mixed solvent mixed with a solvent having no hydroxyl group may be used as the organic solvent. Examples of solvents having a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Among these, propylene glycol monomethyl ether and lactic acid Ethyl ester is preferred. Examples of solvents having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, 7-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethyl vinylammonium amine, dimethyl subbase, etc., among them propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, 7-butyrolactone, cyclic Hexanone and butyl acetate are preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone are more preferred. The mixing ratio (mass) of a solvent having a hydroxyl group and a solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and most preferably 20/80 to 60/40. . In terms of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is more preferable. [7] (G) Alkali-soluble resin The positive-type photoresist composition for liquid immersion exposure of the present invention may further contain a resin soluble in an alkali developer, thereby improving sensitivity. In the present invention, novolak resins having a molecular weight of about 1,000 to 20,000 and polyhydroxystyrene derivatives having a molecular weight of about 3,000 to 50,000 can be used as the resin, but because these have a large absorption for light below 25 Onm 'Therefore, it is better to use it in part of hydrogenation or in an amount of -64- 200534042 which is 30% by mass or less of the total resin content. Further, a resin having a carboxyl group as an alkali-soluble group can be used. Among the resins having a carboxyl group, an alicyclic hydrocarbon group having a monocyclic or polycyclic ring is preferred in order to improve the dry etching resistance. Specific examples include a copolymer of a methacrylic acid ester and a (meth) acrylic acid having an alicyclic hydrocarbon structure having no acid decomposability, or a resin of a (meth) acrylic acid ester having an alicyclic hydrocarbon group having a carboxyl group at a terminal. The amount of the alkali-soluble resin to be added is usually 30% by mass or less based on the total amount of the resin containing the acid-decomposable resin. • [8] (H) Acetic acid sulfonium salt The positive photoresist composition for liquid immersion exposure of the present invention may also contain a carboxylic acid phosphonium salt. Examples of the carboxylic acid key salt of the present invention include a carboxylic acid salt, a carboxylic acid iodide salt, and an ammonium carboxylic acid salt. In particular, the (H) carboxylic acid key salt is preferably an iodine key salt or a salt. In the carboxylic acid sulfonium salt of the present invention, the carboxylate residue is preferably an aromatic group-free carbon-carbon double bond. More preferred anionic moieties are linear, branched, 0 monocyclic or polycyclic alkyl carboxylic acid anions having 1 to 30 carbon atoms. More preferred are anions in which some or all of these alkyl groups are carboxylic acids substituted with fluorine. The alkyl chain may also contain oxygen atoms. This makes it possible to ensure the transparency of light below 220 nm ', to improve sensitivity and resolution, and to improve the density correlation and exposure range. Examples of the anion of the fluorine-substituted carboxylic acid include fluorinated acetic acid, difluorinated acetic acid, trifluorinated acetic acid, pentafluorinated propionic acid, heptafluorobutanoic acid, nonafluorinated pentanoic acid, perfluorinated dodecanoic acid, Perfluorinated tridecanoic acid, perfluorinated cyclohexane residual acid, anion of 2,2-bistrifluoromethylpropionic acid, etc. -65- 200534042 These carboxylic acid phosphonium salts can be synthesized by reacting rhenium hydroxide, iodohydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent. The content of the carboxylic acid key salt in the composition is 0 for all the solid components of the composition. 1 ~ 20% by mass, preferably 0. 5 to 10 mass%, more preferably 1 to 7 mass%. [9] Other additives in the positive type photoresist composition for liquid immersion exposure of the present invention may further contain a dye, a plasticizer, a photosensitizer, and a compound that can promote the solubility in a developing solution, as necessary. (For example, phenol compounds having a molecular weight of less than 1,000, alicyclic and aliphatic compounds having a carboxyl group) and the like. The phenol compound having a molecular weight of 1,000 or less can be easily synthesized by those skilled in the art by referring to methods described in, for example, Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application No. 2-28531, US Patent No. 4,916,210, and European Patent No. 2 1294. Specific examples of alicyclic or aliphatic compounds having a carboxyl group, such as carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantanecarboxylic acid derivatives, adamantane dicarboxylic acid, Cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, and the like are not limited thereto. [10] Pattern forming method The positive-type photoresist composition for liquid immersion exposure of the present invention is to dissolve the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, and then coat the predetermined carrier for use. . In other words, the positive photoresist composition for liquid immersion exposure is coated with a suitable thickness (usually 50-50 nm) -66- 200534042 to a manufacturing method by a suitable coating method such as a spinner or a coater. On a substrate (such as silicon / sand dioxide coating) used for precision integrated circuit components. After coating, the applied photoresist is dried by a spin or baking method to form a photoresist film, and then exposed through a liquid immersion liquid through a patterned photomask or the like (liquid immersion exposure). For example, the photoresist film and the optical mirror are exposed in a state of being filled with a liquid immersion liquid. The exposure amount can be appropriately set, and is usually 1 to 100 mJ / cm2. After exposure, it is preferable to perform rotation or / and baking, development, and washing to obtain a good pattern. The baking temperature is usually 30 ~ 300 ° C. In the case of the PED described above, the shorter the time from exposure to the baking process, the better. Here, the exposure light source is preferably 250 nm or less, and more preferably, far ultraviolet rays of 220 nm or less. Specifically, for example, KrF excimer laser (24 8 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-ray, etc., ArF excimer laser (193 nm) is more preferable. In addition, the performance change seen when the photoresist is used in liquid immersion exposure is the origin of the photoresist surface in contact with the liquid immersion liquid. The liquid immersion liquid used in the liquid immersion exposure is described below. The liquid immersion liquid is transparent to the exposure wavelength and minimizes the distortion of the optical image projected on the photoresist. A liquid with a temperature coefficient of refractive index as small as possible is preferred, especially the exposure light source is an ArF excimer thunder. In the case of radiation (wavelength; 193 nm), in addition to the above-mentioned viewpoints, it is preferable to use water in terms of availability and handling. When using water as the liquid immersion liquid, in order to reduce the surface tension of water and increase the interfacial active force, only the photoresist layer on the wafer will not be dissolved, and it will affect the optical coating under the mirror -67- 200534042 element Additives (liquid) can be added in negligible proportions. The additive is preferably an aliphatic alcohol having a refractive index almost equal to that of water, and specific examples thereof include methanol, ethanol, and isopropanol. By adding an alcohol having a refractive index equal to that of water, even if the concentration of the alcohol component in the water changes due to evaporation, the refractive index change of the entire liquid is extremely small. In addition, when a substance that is opaque to 193 nm light or an impurity having a refractive index different from that of water is mixed, the optical image projected on the photoresist is deformed. Therefore, distilled water is preferred. Alternatively, pure water filtered through an ion exchange filter ® can be used. The resistance of water is 18. 3MQcm or more is preferred, TOC (organic matter concentration) is preferably 20ppb or less, and degassing treatment is preferred. In addition, lithography performance can be improved by increasing the refractive index of the liquid immersion liquid. In this regard, an additive for increasing the refractive index may be added to water, and heavy water (D20) may be used instead of water. When the photoresist film of the positive type photoresist for liquid immersion exposure of the present invention and the liquid immersion φ liquid are used, in order to prevent the photoresist film from directly contacting the liquid immersion liquid, a liquid immersion liquid insoluble film (hereinafter referred to as "Surface Coating"). The necessary functions of surface coating are coating suitability for the upper layer of the photoresist, transparency to radiation (especially 193 nm), and poor solubility in liquid immersion liquid. The surface layer is coated so as not to be mixed with the photoresist, and can be evenly applied to the upper layer of the photoresist. In terms of 193nm transparency, the surface layer is preferably coated with an aromatic-free polymer, such as a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a silicon-containing polymer, Fluorinated Polymer-68-200534042 etc. When the surface coating is peeled off, a developing solution may be used, or another peeling agent may be used. The release agent is preferably a solvent having a small penetration into the photoresist. The peeling process is preferable because it can be processed at the same time as the photoresist developing process. For peeling with an alkali developing solution, the surface layer is preferably coated with an acid, but it can be neutral or alkaline in terms of non-internal miscibility with the photoresist. The smaller the difference in refractive index between the surface coating and the liquid immersion solution, the higher the resolution. When the exposure light source is ArF excimer laser (wavelength: 193nm), it is better to use ® water as the liquid immersion liquid, so the surface layer of ArF liquid immersion exposure is coated with a refractive index close to that of water (1. 44) is better. Further, it is preferable to use a thin film in terms of transparency and refractive index. The following developing solution was used in the developing process. As the developer of the positive photoresist composition for liquid immersion exposure, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, ethylamine, n-propylamine, etc. can be used. Equal primary amines, secondary amines such as diethylamine, di-n-butylamine, tertiary amines such as triethylamine, φ methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, etc. , Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and pipe trap, and other alkaline aqueous solutions. In addition, an appropriate amount of an alcohol or a surfactant can be added to the alkaline aqueous solution and used. The cleaning solution can be used with pure water or by adding an appropriate amount of a surfactant. The alkali concentration of the alkali imaging solution is usually 0. 1 to 20% by mass. The pH value of the alkali imaging solution is usually 10. 0 ~ 15. 0. -69- 200534042 In addition, after the development process or cleaning process, a process for removing the developing solution or cleaning solution adhering to the pattern by a supercritical fluid may be performed. [Embodiment] [Example] In the following, the present invention will be described in more detail by way of examples, but the content of the present invention is not limited by these. Synthesis Example 1 (Synthesis of Resin (24)) A mixture of norbitanecarboxylic acid 3-butyl ester, norbitanecarboxylic acid, norbitanecarboxylic acid 2-®hydroxyethyl ester, and maleic anhydride was dissolved in tetrahydrofuran. , A solution with a solid content of 50% by mass is prepared. This was charged into a 3-necked flask, and heated under a nitrogen gas flow at 60 ° C. The reaction temperature was stabilized, and 5 mol% of the free radical starter V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then charged into a 5 times amount of hexane in the reaction solution to precipitate a white powder. This material was re-dissolved in tetrahydrofuran and put into 5 times the amount of hexane in the solution to precipitate a white powder. The precipitated φ powder was taken out by filtration and dried to obtain the target resin (24) having the following repeating unit. When the obtained resin (24) was subjected to molecular weight analysis (RI analysis) by GPC, it was 7 900 (weight average) in terms of polystyrene. Similarly, the following resins (1) to (23), (25), and (26) were prepared. • 70- 200534042

Mw = 9900 Μ w / Mn = 1 · 99 1.5Μ0 · 3 equivalents

Mw = 1 0200 Mw / Mn = 1.98 1.2M (Γ3 milliequivalents

Mw = 8900 M w / Mn = 2 .1 0 9.6χ1 (Γ4 milliequivalents -71- 200534042

Mw = 8300 M w / Mn = 1 · 97 1.1χ1〇_3 milliequivalents

M w / Mn = 1. 9 8 8 · 9χ 1 (T4 milli-equivalent

MW = 9700 Mw / Mn = 2.0 1 1.5M (T3 milli-equivalent

-72- 200534042 M w = 8 2 0 0 Mw / Mn = 1.91 l.〇xl (T3 milli-equivalent m M w = 9 5 0 0 Μ w / Mn = 2.07 reference 1 · 9χ1 (T3 milli-equivalent

A-c m

Mw = 1 0300 M w / Μ n = 2.1 6 8.3xlO_4 milliequivalents

M w = 8 7 00 Mw / Mn = 2.21 1.4x 1 (T3 milli-equivalent 200534042

M w = 8 7 0 0 Mw / Mn = 2.21 2.〇x 1 (T3 milli-equivalent

Mw = 1 0200 Mw / Mn = 2.31 2.3x10 "milliequivalents

M w = 8 7 0 0 Mw / Mn = 2.05 3.7x 1 (T3 milli-equivalent

Mw = 8900 M w / Mn = 2.1 1 8.2x 10 "milliequivalents -74- 200534042

Mw = 1 0 400 M w / Mn = 2 · 5 1

M w = 8 1 0 0 Mw / Mn = 2.50 9.6x10 "milliequivalents

M w = 7 9 0 0 Mw / Mn = 2.33 8.〇χ 10 4 milliequivalents

-75- 200534042

Mw = 12100 Mw / Mn = 2.32 2.〇χ 1 (T3 milli-equivalent

M w = 9 7 0 0 Mw / Mn = 1.97 0 milliequivalents

Mw = l 1500 Mw / Mn = 2.00 0 milliequivalents -76- 200534042

M w = 8 4 0 0 Mw / Mn = 2.12 0 milliequivalents

Mw = 9900 M w / Μ η = 1.77 0 milliequivalents

OH

Mw = 7 900 1 .4χ 1 (T3 milli-equivalent-77- 200534042 ch3 4-οη2-ο-P33 (25) o 丄.

Μ w = 9 9 0 0 Μ w / Mn = 1.99 5. 1 χ 1 (T3 milliequivalents

Mw = 1 0200 Mw / Mn = 1.98 5.8 x 10'3 milliequivalents [Examples 1 to 20 and Comparative Examples 1 to 4] < Photoresist adjustment > The components shown in Table 1 below were dissolved in a solvent and adjusted. A solution having a solid content concentration of 10% by mass was filtered through a 0.1 μm polyethylene filter to adjust the positive photoresist solution. The prepared positive photoresist solution was evaluated by the following method, and the results are shown in Table 1. The ratio of each component in Table 1 when using several types is the mass ratio. In the following, the codes of Table 1 are as follows. The acid generator corresponds to the one exemplified above. N-1: Ν, Ν-dibutylaniline-78- 200534042 N-2: N, N-dipropylaniline N_3: N, N-dihydroxyethylaniline N-4: 2,4,5 -tris Phenylimidazole N-5: Hydrogenated antipyrine W -1: Mekafak f 丨 7 6 (made by Dainippon Ink Chemical Co., Ltd.) (fluorine-based) W-2: Mekafak R08 (Da Nihon Ink Chemical Industry Co., Ltd.) (fluorine-based and silicon-based) W-3: Polysiloxane polymer KP-341 (Shin-Etsu Chemical Industry Co., Ltd.) (silicon-based) W-4: Dayton Long Yi Luolu S-366 (made by Dun Luo Yi Ken Mikalu (stock)) SL-1: cyclopentanone SL-2: cyclohexanone SL-3: 2-methylcyclohexanone SL-4: propylene glycol Monomethyl ether acetate SL-5: propylene glycol monomethyl ether SL-6: 2-heptanone SL-7: r-butyrolactone SL-8: propylene carbonate 1-1: lithocholic acid 3-butyl Esters I-2: Amantadine Carboxylic Acid 3-Butyl Ester [Exposure range] Coat an organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd. -79- 200534042) on a silicon wafer, and bake at 20 5 ° C 60 seconds to form a 78 nm anti-reflection film. A modulated photoresist composition was coated thereon, and baked at 115 ° C for 60 seconds to form a 2 50 nm photoresist film. After forming clay on the obtained wafer and treating it with pure water for 60 seconds, it was pattern-exposed using an ArF excimer laser scanner (PAS5 00/1 1 00, N A 0.7 5 manufactured by ASLM). In addition, pure water treatment was performed for 60 seconds after exposure (wet exposure). Then, it was heated at 150 ° C for 90 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 60 seconds, washed with pure water, and then spin-dried to obtain a photoresist pattern. For comparison, exposure (dry exposure) was performed before and after exposure without pure water treatment, and a photoresist pattern was prepared under the same conditions as described above. Take the exposure amount of the mask pattern reproduced by the line and gap of the line width 110nm as the optimal exposure amount, and obtain the exposure amount width that allows the pattern size to be 110nm ± 10% when changing the exposure amount, and divide this frame by the optimal exposure amount. Expressed as a percentage. The larger the threshold, the smaller the performance due to the change in the exposure amount, and the better the exposure range. [Development time dependence] An organic anti-reflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was coated on a silicon wafer, and baked at 205 ° C for 60 seconds to form a 78-nm anti-reflection film. A modulated photoresist composition was coated thereon, and baked at 115 ° C for 60 seconds to form a 150nm photoresist film. The obtained wafer was subjected to two-beam interference exposure (wet exposure) using water as the immersion liquid, and using the device 8 shown in Fig. 1 using a diamond mirror 8 forming a mask pattern of a 11 nm line and a gap. The laser wavelength is 193nm. After heating at -80-200534042 at 120 ° C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 60 seconds, washed with pure water, and then spin-dried to obtain a photoresist pattern. In the exposure amount that reproduces the mask pattern size of the line and gap of 1 Onm when the development time is 30 seconds, the formation size of the same pattern when the development time is 90 seconds is the size difference from llOnm when the side length is (nm )As shown in Table 1. The smaller the size difference, the smaller and better the correlation of development time. For comparison, the same evaluation as described above was performed without exposure to liquid immersion (dry exposure). In the device shown in Fig. 1, 1 represents laser, 2 represents twist, 3 represents shutter, 4, 5, and 6 represent mirrors, 7 represents collector, and 8 represents diamond. Mirror, 9 is a liquid immersion liquid, 10 is a wafer provided with an anti-reflection film and a photoresist film, and 丨 丨 is a wafer stage.

200534042 Table 1

Composition Exposure Range (%) Image-related Tera resin (2g) Photoacid generator dissolution preventing compound (O.lg) Solvent basic compound (4mg) Surfactant (5mg) Dry exposure Wet exposure Dry exposure Wet Exposure example 1 1 Z1 20mg 8ί-2 / 5ί-4 = 50/50 Nl Wl 13.2 13.0 3.3 4.2 2 2 Z2 24mg SL-2 / SL-4 = 40/60 N-2 Wl 13.5 13.1 3.2 3.2 3 3 Z2 32mg SL-2 / SL-4 = 40/60 N-2 Wl 12.5 13.4 3.4 3.2 4 4 Z14 20mg SL ^ ISL-AMOm 'If Η * J \\\ W-4 11.8 11.7 3.3 3.6 5 5 Z2 20mg SL -2 / SL-4 = 40/60 N-2 None 12.4 13.5 3.5 3.1 6 6 Z24 20mg SL ^ / SL-A / SL · ^ 40/59/1 Nl / N-3 = l / l W-4 13.0 12.8 3.4 4.0 7 7 Z2 20mg / Z9 15mg SL-2 / SL-4 = 50/50 Nl W-2 12.8 12.4 3.6 3.9 8 8 Z16 20mg SL-2 / SL-5 = 70/30 N-3 / N- 5 = l / l W-3 12.9 12.4 3.8 4.0 9 9 Z38 30mg SL-2 / SL-4 / SL-8 = 40/59/1 N-2 Wl 13.1 13.2 3.8 3.1 10 10 Z2 25mg SL-2 / SL -4 = 40/60 N-2 W-2 13.0 13.9 3.6 3.0 11 11 Z32 12mg / Z1 25mg SLd / SI ^ MOMO N-3 W-3 14.0 13.2 3.6 3.1 12 12 Z31 lOmg SL-2 / SL-4 = 40/60 Nl W-4 14.1 14.1 3.1 3.2 13 13 Z15 30mg 1-1 SL-l / SL-6 = 40/60 N-5 W-4 12.9 11.1 3.6 3.2 14 14 Z15 32mg SL-4 / SL-5 = 60/40 Nl Wl 13.4 13.0 3.8 4.0 15 15 Z38 40mg SL-3 / SL-6 = 60/40 N-4 / N-5 = l / l W-3 13.6 13.1 4.0 4.2 16 16 Z27 33mg SLAISLA / SL-l ^ 40/58/2 Nl W-2 12.7 12.6 3.5 3.8 17 17 Z36 50mg 1-2 SL-2 / SL- 6 = 60/40 N-2 W-2 13.0 12.8 3.8 4.0 18 18 Z24 27mg SL-2 / SL-6 = 60/40 N-4 / N-5 = l / l Wl 13.2 13.0 4.1 3.8 19 19 Z13 29mg / Z9 15mg SL-4 / SL-5 = 50/50 > fnf Wl 12.7 12.1 4.0 3.2 20 24 Z18 25mg SL-2 / SL-4 = 40/60 N-3 W-4 12.6 12.4 3.5 4.1 Comparative Example 1 20 Z2 24mg SL-4 / SL-5 = 50/50 Nl Wl 13.1 2.2 3.6 10.0 2 21 Z2 24mg SL-4 / SL-5 = 50/50 Nl Wl 12.5 3.8 3.7 12.0 3 22 Z2 24mg SL-4 / SL -5 = 50/50 Nl Wl 14.0 2.6 4.2 10.2 4 23 Z2 24mg SL-4 / SL-5 = 50/50 Nl Wl 13.8 2.4 4.2 11.4 5 25 Z2 24mg SL-4 / SL-5 = 50/50 Nl Wl 12.1 2.8 3.2 10.5 6 26 Z2 24mg SL-4 / SL-5 = 50/50 Nl Wl 12.5 3.0 3.8 10.7 -82- 200534042 From the above results, it can be seen that the positive photoresist composition for liquid immersion exposure of the present invention is When the pattern is formed by liquid immersion exposure, the exposure range is wide and the development time is related With good performance. [Simplified description of the drawing] Figure 1 is a schematic diagram of a two-beam interference exposure experimental device. [Description of Symbols of Main Components] 1 Laser 2 Twist 3 Fast Gates 4,5,6 Mirror 7 Set Light Mirror 8 Prism 9 Liquid Immersion Liquid 10 Crystal Circle 11 Crystal Circle Table -83-

Claims (1)

200534042 10. Scope of patent application: 1. A positive photoresist composition for liquid immersion exposure, characterized by containing (A) OH valence of 0.000 1 ~ 0.005 milli-equivalent, and having monocyclic or polycyclic alicyclic hydrocarbon structure Resins that increase the solubility in alkaline imaging solutions by the action of acids, and (B) Compounds that generate acids by irradiation with active light or radiation. 2. A pattern forming method, which is characterized in that a photoresist film is formed by using a positive photoresist composition as described in item 1 of the patent application scope, and the photoresist film liquid is immersed, exposed and developed. -84-