TW200844664A - Positive resist composition and pattern forming method - Google Patents

Abstract

A positive photosensitive composition comprises: (A) a resin that has an acid decomposable repeating unit represented by formula (I) and increases its solubility in an alkali developer by action of an acid: (B) a compound generating an acid upon irradiation with actinic light or radiation; (C) a hydrophobic resin insoluble in an alkali developer and having at least either one of a fluorine atom and a silicon atom; and (D) a solvent, wherein in the formula (I), Xa1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, Ry1 to Ry3 each independently represents an alkyl group or a cycloalkyl group, and at least two of Ry1 to Ry3 may be coupled to form a ring structure, and Z represents a divalent linking group.

Description

'200844664 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a manufacturing process for a semiconductor (such as 1c), a circuit board for a liquid crystal, a heating head, and the like, and other lithography steps for light manufacturing. A positive-type photoresist composition, and a pattern forming method using the composition. In particular, the present invention relates to a positive-type photoresist composition suitable for exposure to an immersion type projection exposure apparatus using a far-ultraviolet light having a wavelength of 300 nm or less as an exposure light source, and a composition using the same Figure # Case formation method. [Prior Art] The trend of refining semiconductor components has led to a shortening of the exposure wavelength and an increase in the number of apertures (NA) of the projection lens. As a result, an exposure apparatus having an NA of 0.84 and using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. As can be seen from the following expressions, the resolution and depth of focus can be expressed by the following equation: (resolution) = k "(X/NA) _ (focus depth) = ± k24 / NA2 where λ is the exposure wavelength, ΝΑ The number of apertures of the projection lens, and kl and k2 are coefficients for this method. In order to enhance the resolution by further shortening the wavelength, an exposure apparatus using a F2 excimer laser having a wavelength of 157 nm as a light source is being investigated. Since the materials for lenses and the materials for photoresist used in exposure equipment are strictly limited, it is very difficult to stabilize the manufacturing cost of the equipment or materials and to stabilize their quality. Therefore, it is impossible to provide sufficient performance and stability within the required time. Qualitative exposure equipment and the possibility of photoresist. As for the technique of enhancing the resolution of an optical microscope, a so-called impregnation method is known in which a high refractive index liquid is filled between a projection lens and a sample (hereinafter referred to as "impregnation liquid" Method). This "dip" has the following effects. Assuming that the exposure wavelength in air is λ〇, the refractive index of the immersion liquid is η with respect to air, and the convergence half angle of the light is q and NA〇= sine, the resolution and depth of focus during impregnation can be expressed by the following equation: # (analysis Degree) = 1^. (human. / 11) ^ 八 0 (focus depth) = ± k2. (X0 / n) / NA02 This indicates that the immersion produces the same effect as the exposure using the wavelength 1 / η. In other words, assuming that the same optical projection system is used, the depth of focus can be made n times larger by dipping. It is effective for any pattern shape. Therefore, the impregnation can be combined with a super-analytical technique that is currently being studied, such as a phase shift method or an off-axis illumination method. Examples of the apparatus for transferring the fine image pattern of the semiconductor device by the above effects include those described in JP-A-5 7-1 5 3 43 3 and the like. Recent progress in immersion exposure technology is reported in The International Society for Optical Engineering (SPIE Proc.), 4688, 1 1 (2002) > J. Vac. Sci. TecnoL, B 1 7 (1 999), The Proceedings of The International Society for Optical corpse / five iVocJ, 3999, 2 (2000) and so on. When using an ArF excimer laser as a light source, pure water (refractive index at 193 nm: 200844664 1.44) is derived from the viewpoint of processing safety and transmittance and refractive index at 193 nm. For the most promising impregnating liquid. Considering the balance between the penetration rate and the refractive index at 157 nm, the fluorine-containing solution is being investigated as an immersion liquid for exposure using a F 2 quasi-molecular laser as a light source. However, no impregnating liquids with satisfactory environmental safety and refractive index were found. Judging by the degree of impregnation and the maturity of the photoresist, the immersion exposure technique will be used first for ArF exposure equipment. Since the discovery of photoresists for KrF excimer lasers (248 nm) has been used, a chemical amplification method has been used as a photoresist image formation method to compensate for the decrease in sensitivity due to light absorption. For example, an image forming method using positive chemical amplification is a method of exposing a photoresist to cause decomposition of an acid generator in an exposed region and generating an acid, and subjecting the resulting photoresist to post-exposure baking (PEB) to utilize the acid thus produced as The reaction catalyst converts the alkali-insoluble group into an alkali-soluble group, and develops the exposed region by alkali development. As for the chemically amplified photoresist composition, a composition obtained by mixing two or more resins having a specified structure is proposed, for example, in the patent of W Ο 2 0 0 5 / 0 0 3 1 8 8 and JP - A - 2 0 0 2 - 3 0 3 9 7 8 patent. Although the ArF excimer laser photoresist using a chemical amplification mechanism has recently become a primary photoresist, it needs to be improved because pattern collapse occurs when it is exposed through a mask of a very small mask size. It has been pointed out that when the chemically amplified photoresist is immersed and exposed, the contact of the photoresist layer with the impregnating liquid during exposure causes the photoresist layer to degrade or the component to diverge from the photoresist layer, which adversely affects the immersion liquid. International Publication No. WO 2004/068242 describes an example of a change in photoresist resistance caused by immersion of a photoresist by ArF exposure in water before and after exposure, and indicates that this change is a problem of immersion exposure. In an immersion exposure method, the 200844664 exposure using a scanning type immersion exposure apparatus requires the movement of the immersion liquid to coincide with the movement of the lens. If not, the exposure speed is reduced, which can negatively affect productivity. When the immersion liquid is water, it is desirable that the photoresist film be hydrophobic and have good water followability. In addition, it is actually difficult to find a suitable combination of a resin, a photoacid generator, an additive, and a solvent which can satisfy the integration performance of the photoresist. When a fine pattern having a line width of 100 nm or less is formed, even if the resolution performance is excellent, pattern disintegration occurs during the manufacture of the device, which may cause defects. Therefore, it is necessary to overcome the pattern collapse and reduce the line edge roughness (disturbing the uniform line pattern formation). Φ The term "line edge thickness" means that the line pattern of the photoresist and the edge of the substrate interface are irregularly formed in the direction of the vertical line due to the photoresist property. This pattern appears to have concave and convex edges (about ± nanometers to tens of nanometers) from the top. Since these concavities and convexities are transferred to the substrate in the etching step, large irregularities may deteriorate electrical properties, resulting in a decrease in yield. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist composition which is small in thickness of a line due to normal exposure or immersion exposure, and which is excellent in water following force during immersion exposure; and a composition using the same The pattern forming method of the object. < 1 > A positive-type photoresist composition comprising: (A) a resin having an acid-decomposable repeating unit represented by the formula (I) and increasing its solubility in an alkali developer by the action of an acid; (B) a compound which produces an acid upon irradiation with light-like radiation or radiation; (C) a hydrophobic resin which is insoluble in an alkali developer and has at least one of 200844664 fluorine atom and germanium atom; and (D) species Solvent:

Wherein in formula (I),

Xa! represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom,

Ryi to Ry3 each independently represent a yard or a ring base, and at least two of 1?1 to Ry3 may be joined to form a ring structure, and Z represents a divalent bond. &lt;2&gt; The positive resist composition according to the above <1>, wherein Z in the formula (1) is a divalent linear hydrocarbon group or a divalent cyclic hydrocarbon group. &lt;3&gt; The positive resist composition according to the above <1> or <2>, wherein the resin (A) further has at least one member selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and an acid group. The repeating unit of the base. The positive resist composition of any one of the above-mentioned <1> to <3>, wherein the compound (B) comprises a compound which generates an acid represented by the formula (BII):

(Rb^n (BH) where in the formula (BII),

Rh represents a group having an electron attracting group, Rb2 represents an organic group having no electron attracting group, and 200844664 m and n each represent an integer of 〇 to 5, and the condition is m + n$5, and when m is 2 or more, plural The |^ may be the same or different, and when η is 2 or more, the plurality of Rb2 may be the same or different. &lt;5&gt; The positive resist composition according to the above <4>, wherein in the formula (BII), the melon is 1 to 5 and the electron attracting group of Rb1 is at least one selected from the group consisting of a fluorine atom and a fluoroalkyl group. An atom or a group of a nitro group, an ester group, and a cyano group. The positive-type photoresist composition of any one of the above-mentioned <1> to <5>, wherein the resin (C) has at least one selected from the group consisting of the formulas di), (1-2) and U-3 The repeating unit of the fluorine-containing repeating unit, which is stable in acid and insoluble in alkali developer:

(1-1) (1-2) (1-3) wherein in the formulae (1-1) to (1-3),

Ri represents a hydrogen atom or an alkyl group, R2 represents a fluorine-based group, R3 represents a hydrogen atom or a monovalent organic group, and IU to R7 each independently represent a hydrogen atom, a fluorine atom, a hospital group, and a methoxy group, and the condition is R4 to At least one of them represents a fluorine atom, or ^ and R5 or R6 and R? may be bonded to form a ring,

Rs represents a hydrogen atom, a fluorine atom or a monovalent organic group.

Rf represents a fluorine atom or a monovalent organic group having a fluorine atom, -10- 200844664 L represents a single bond or a divalent bond group, Q represents an alicyclic structure, and k is an integer of 0 to 3. The positive-type resist composition according to any one of <1> to <5>, wherein the resin (C) has a fluorene-containing repeating unit represented by the formula (CI) and is a formula (C II) Represents at least one of the hydrazine-containing repeating units, which is stable in acid and insoluble in alkali developer: R〇i Rc1

Lc

Rc2 R〇2 (CU) where in the formulas (CI) and (CII),

Lc represents a single bond or a divalent bond,

Rq each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group.

Rc2 represents a monovalent organic group having at least one deuterium atom,

Rc3 represents a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, Q c represents an alicyclic structure, and kc is an integer of 0 to 3. The positive-type photoresist composition of any one of the above-mentioned <1> to <5>, wherein the resin (C) is at least one of the following: (C1) one having: a fluorine atom and a ruthenium atom At least one; and an alicyclic structure resin; and -11- 200844664 (C2) - a repeating unit having at least one of a fluorine atom and a halogen atom in a side chain thereof; and an unsubstituted group in a side chain thereof A resin of a repeating unit of an alkyl group. &lt;9&gt; The positive resist composition of any one of &lt;1&gt; to &lt;8&gt;, which is used for exposing light having a wavelength of 200 nm or less. The positive-type resist composition according to the above <4> or <5>, wherein in the formula (BII), the organic group having no electron-attracting group of Rb2 is a group having an alicyclic group. And a positive-type photoresist composition according to any one of the above <1> to <1>, which further comprises (E) a basic compound. &lt;12&gt; The positive-type photoresist composition according to the above &lt;1 1&gt;, which contains at least one of 2,6-diisopropylaniline and tetramethylammonium hydroxide as the basic compound (E) 〇&lt; The positive-type photoresist composition of any one of the above-mentioned &lt;&gt; to &lt;12&gt;, which contains at least one of propylene glycol monomethyl ether acetate, 2-heptanone and γ-butyrolactone As solvent (D). The positive-type photoresist composition of any of the above-mentioned <1> to <13>, which further comprises (F) a surfactant. &lt;1 5&gt; A pattern forming method comprising: forming a photoresist film from the positive resist composition of any of the above &lt;1&gt; to &lt;14&gt;; and exposing and developing the photoresist film. The pattern forming method according to the above <15>, wherein the photoresist film is exposed to the immersion liquid. [Embodiment] -12- 200844664 Hereinafter, the present invention will be specifically described. In the present specification, when a group (a primary group) is represented by a substitution or an unsubstituted, the group includes a group having no substituent and a group having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). (A) Resin which increases its solubility in an alkali developer by the action of an acid. The resin which is used in the positive-type resist composition of the present invention to increase its solubility in an alkali developer by the action of an acid has the following formula (1) a resin represented by an acid-decomposable repeating unit (which may be referred to as "resin of component (A)"):

Xai

Wherein in formula (I),

Xai represents no hydrogen atom, sulfhydryl group, cyano group, or halogen atom,

Ryi to Rys each independently represent an alkyl group or a cycloalkyl group, or at least two of Ryi to Ry3 may be bonded to form a monocyclic or polycyclic cyclic hydrocarbon structure, and Z represents a divalent linking group. In the formula (I), the alkyl group of &amp; 1 may be substituted with a hydroxyl group, a halogen atom or the like. Xw is preferably a hydrogen atom or a methyl group.

The alkyl group of Ryi to Rys may be a linear alkyl group or a branched alkyl group. Its q stomach has a substituent. Examples of the substituent which it may have include a fluorine atom, a chloroogen+, a bromine atom, a hydroxyl group, and a cyano group. The linear or branched alkyl group is preferably a Ci-based group, and the 13-200844664 is more preferably a CL4 alkyl group. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl, preferably methyl and ethyl. Examples of the cycloalkyl group of 11? to Ry3 include a monocyclic C3_8 cycloalkyl group and a polycyclic 4-cycloalkyl group. It may have a substituent. Preferred examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group and a cyclopropyl group. Preferred examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a tetracyclododecyl group, a tricyclodecyl group, and a bis-damantyl group. The monocyclic hydrocarbon structure formed by linking at least two of Ryi to Ry3 is preferably a ring #pentyl or a cyclohexyl group. The polycyclic hydrocarbon structure formed by linking at least two of Ryi to Ry3 is preferably an adamantyl group, a decyl group or a tetracyclododeca group. Z is preferably a divalent linear hydrocarbon group or a divalent cyclic hydrocarbon group. It can have a substituent. Examples of the substituent which it may have include a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, and a cyano group. Z is preferably a divalent ChM bond group, more preferably a linear Ci.4 alkylene group or a cyclic C5_2G alkylene group, or a combination thereof. Examples of the linear Ci-4 alkylene group include a methylene group, an ethyl group, a propyl group, and a butyl group. It can be linear or branched. It is preferably a methylene group. Examples of the ring C5.20 alkylene group include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a decyl group and an adamantyl group. It is an adamantyl group. The polymerizable compound for forming the repeating unit represented by the formula (I) can be easily synthesized by a known method. For example, it can be reacted with a carboxylic acid halide compound under basic conditions in a similar manner as described in JP-A-2 00 5-3 3 1 9 1 8 'and then the reaction product and the carboxylic acid compound in the base Synthesis under the conditions of the reaction, as shown in the following reaction chart: -14- 200844664

Preferred examples of the repeating unit represented by the formula (I) are shown below, but the invention is not limited thereto. In the formula, xai represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

200844664

-16- 200844664

The repeating unit represented by the formula (1) decomposes due to the action of an acid and produces a carboxylic acid. As a result, it increases the solubility of the resin in the alkali developer. The resin of the component (A) may have other acid-decomposable repeating units in addition to the acid-decomposable repeating unit represented by the formula (I). The acid-decomposable repeating unit other than the acid-decomposable repeating unit represented by the formula (I) is preferably a repeating unit represented by the following formula (II):

Xat

In formula (II),

Xai represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, and is similar to Xai in the formula (I).

Rxi to Rx3 each independently represent an alkyl group or a cycloalkyl group. At least two of RX1 to Rx3 may be bonded to form a cycloalkyl group. As for the alkyl group of Han~~rX3, it is preferably a linear or branched Cl_4 alkane-17-200844664 base such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and third. Butyl. As the cycloalkyl group of RXi to rX3, it is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclic fluorenyl group or a tetracyclododecanyl group. With adamantyl. As for the cycloalkyl group formed by linking at least two of Rxi to Rx3, it is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclic fluorenyl group, or a fourth group. Cyclododecyl and adamantyl. • These groups shown as Rxi to RX3 may further have a substituent. Examples of the substituent which may be possessed include a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, and a cyano group. With respect to the preferred mode of Rxi to RX3, RXl represents a methyl group or an ethyl group and RX2 is bonded to Rx3 to form the above monocyclic or polycyclic cycloalkyl group. The following is a specified example of a repeating unit having an acid-decomposable group, but the present invention is not limited thereto. -18- 200844664 (Rx means H, CH3 or CH2OH, and Rxa and Rxb each represent c^4

alkyl)

The repeating unit represented by the formula (II) is preferably the repeating units 1, 2, 10, 11, 12, 13, and 14 in the above designated examples. When the acid-decomposable group repeating unit represented by the formula (I) is used in combination with other acid-decomposable group repeating units (preferably, the repeating unit represented by the formula (II) is -19-200844664), Represents the acid-decomposable group repeating unit: the ratio of the other acid-containing decomposable groups repeating a single enthalpy is from 90:10 to 10:90, more preferably from 80:20 to 20:8 0 〇 component (A) The total content of the acid-decomposable group repeating unit in the resin is preferably from 20 to 50 mol%, more preferably from 25 to 45 mol%, based on all the repeating units in the polymer. The resin of the component (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone group, a trans group, a cyano group, and an alkali-soluble group. The resin of the component (A) is preferably a repeating unit having a lactone structure. Although the lactone structure is not limited at all, it is preferably a 5- to 7-membered ring vinegar structure, preferably a 5- to 7-membered ring lactone which is condensed with other ring structure rings to form a bicyclic structure or a spiro structure. structure. More preferably, it is a resin having a repeating unit having a lactone structure represented by any of the following formulae (LC1_1) to (LC1-16). The lactone structure can directly bond the backbone. Preferably, the vinegar structure comprises (LC1-1), (LC1-4), (LC1-5), (L(n-6), (LC1·13), and (LC 1-1 4). The lactone structure reduces line edge roughness and development defects. -20 - 200844664

The LCl-16 lactone moiety may have a substituent (Rb2) or no substituent. Preferable examples of the substituent (Rh) include Ci.8 alkyl, 匕7-cycloalkyl, alkoxy, Ci-8 alkoxycarbonyl, carboxyl, halogen atom, hydroxyl group, cyano group, and acid-decomposable group. . More preferred examples include c i _4 alkyl, cyano and acid decomposable groups. In the above formula, η2 represents an integer from 〇 to 4. When "2 or more, a plurality of Rb2 may be the same or different, or a plurality of substituents Rb2 may be bonded to form a ring. There is a lactone structure represented by any one of formulas (LC1-1) to (LC1-16) Examples of the repeating unit include a repeating unit represented by the following formula (AI): 200844664

(AI)

COO-Ab-V in the formula (AI),

Rb〇 represents a hydrogen atom, a halogen atom or a CW4 alkyl group. Preferable examples of the substituent which the alkyl group of Rb〇 may have include a hydroxyl group and a halogen atom.

Examples of the halogen atom of RbG include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb〇 is preferably a hydrogen atom or a methyl group. • Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group including a combination thereof. It is preferably a single bond or a divalent bond represented by -Ah-C02-. Ab! is a linear or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexyl group, an adamantyl group, or a decyl group. V represents a group having a structure represented by any of the formulae (LC-1) to (LC-16). Repeating units having a lactone structure generally have optical isomers. It can use any of these optical isomers. The optical isomers can be used singly or in combination. When an optical isomer is mainly used, it preferably has an optical purity (ee) of 90 or more, more preferably 95 or more. The content of the repeating unit having a lactone structure is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, based on all the repeating units in the polymer, and still more preferably from 30 to 50. Moer%. The following is a specified example of a repeating unit having a lactone structure', but the present invention is not limited thereto. -22- 200844664 (Rx means H, CH3, CH2OH, or CF3)

-23- 200844664 (Rx means H, CH3, CH2〇H, or CF3)

-24- 200844664 (Rx means H, CH3, CH2OH, or CF3)

As for the repeating unit having a lactone structure, it is particularly preferably the following repeating unit. The choice of the optimum lactone structure improves the shape of the pattern and the thickness/fineness dependence. (Rx means H, CH3, CH2OH, or CF3) -25- 200844664

The resin of the component (A) preferably has a hydroxyl group-containing or cyano group repeating unit. The resin having this repeating unit has improved substrate adhesion and developer affinity. The hydroxyl group- or cyano group-containing repeating unit is preferably a repeating unit having a hydroxy or cyano group substituted alicyclic hydrocarbon structure. The alicyclic hydrocarbon structure in which the alicyclic hydrocarbon structure is substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group or a norbornyl group. Preferably, the hydroxy or cyano substituted alicyclic hydrocarbon structure is preferably a partial structure represented by any of the following formulas (Vila) to (Vlld):

In the formulae (Vila) to (Vile), R2c to R4c each independently represent a hydrogen atom, a hydroxyl group or a cyano group, and a condition that at least one of R2C to R4C represents a hydroxyl group or a cyano group. It is preferably one or two of r2C to R4C which is a hydroxyl group, and the balance is a hydrogen atom. More preferably in the formula (VIIa) -26- 200844664, the unit of R2C to R4C each represents a hydroxyl group, and the rest represents a hydrogen atom having a partial structure represented by the formulas (Vila) to (VIId) including each Repeating unit represented by formula (Alla) to (AIId)

(Alla) (Allb) (AIIc) (Alld;

In the formula (Alla) to (Allb),

Ric represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group q R2C to R4C having the same meaning as R2c in the formulas (Vila) to (Vlld). The repeating unit having a hydroxyl group or a cyano group substituted alicyclic hydrocarbon structure is preferably 5 to 40 mol%, 5 to 30 mol%, and most preferably 10 to 25 mol%. The following are designated examples of hydroxyl- or cyano-containing repeating units, and are not limited thereto. The content of the 3 base, and the phase of the R4C is better, but the present is -27- 200844664

The resin of the component (A) is preferably a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonylamino group, a sulfonyl sulfoximine group, a bis-sulfonyl fluorenylene group, and an aliphatic alcohol substituted with an electron attracting group at its α-position (for example, hexafluoro group) Isopropyl alcohol). More preferably, it is a resin having a carboxyl group-containing repeating unit. When the resin has a repeating unit having an alkali-soluble group, it enhances the resolution at the time of forming a contact hole. As the repeating unit having an alkali-soluble group, it is preferably a repeating unit having an alkali-soluble group directly bonding a resin main chain (such as an acrylic acid or methacrylic repeating unit), and a base having a bonded-bonding resin main chain A repeating unit of a soluble group, and an S complex unit in which an alkali-soluble group is introduced into a polymer chain terminal at the time of polymerization using an alkali-soluble polymerizable initiator or a chain transfer agent. The linking group may have a monocyclic or polycyclic hydrocarbon ring structure. It is particularly preferably an acrylic or methacrylic repeating unit. The content of the repeating unit having an alkali-soluble group is preferably from 0 to 20 mol%, more preferably from 3 to 15 mol%, most preferably from 5 to 10 mol%, based on all the repeating units in the polymer. The following is a specified example of a repeating unit having an alkali-soluble group, but the present invention is not limited thereto. -28- 200844664

, CH3, CF3, or CH2OH)

With respect to the repeating unit having at least one group selected from the group consisting of a lactone group, a trans group, a cyano group, and a test group, it is more preferred to have at least two selected from the group consisting of an internal hydroxy group, a hydroxyl group, a cyano group, and an alkali-soluble group. The repeating unit of the group is still more preferably a repeating unit having a cyano group and a lactone group. Particularly preferred is a repeating unit having a cyano substituted LC1-4 lactone structure. The resin of the component (A) may further have a repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposition power. The use of a resin having this repeating unit can reduce the release of low molecular components from the photoresist film to the immersion liquid during the immersion exposure. Examples of the repeating unit include 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, and cyclohexyl (meth)acrylate. In addition to the above repeating structural unit 'in order to adjust dry etching resistance, standard developer suitability, substrate adhesion, photoresist shape, and photoresist, it is usually required to be -29-200844664 (such as resolution, heat resistance and sensitivity). The resin of the component (A) may have various repeating structural units. Examples of such repeating structural units include, but are not limited to, repeating units corresponding to the following monomers. The addition of this repeating structural unit can precisely control the properties required for the resin as component (A), in particular, (1) solubility in a coating solvent, (2) film forming properties (glass transfer point), and (3) alkali development Properties, (4) membrane loss (selection of hydrophilic, hydrophobic or alkali-soluble groups), (5) adhesion of unexposed portions to the substrate, (6) dry etching resistance, and the like. Examples of the monomer include a compound having an addition polymerizable unsaturated bond selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, allyl compound, vinyl ether, and vinyl ester. . Further, it may copolymerize an addition polymerizable unsaturated compound which is copolymerizable with a monomer corresponding to the above repeating structural unit. In the resin of the component (A), if necessary, the molar ratio of the repeating structural unit contained in the resin is determined to control the dry etching resistance of the photoresist, the standard developer® application force, the substrate adhesion, and the photoresist shape, And the properties normally required for photoresist (such as resolution, heat resistance and sensitivity). When the positive photosensitive composition of the present invention is used for ArF exposure, the resin of the component (A) preferably has no aromatic group from the viewpoint of transparency to ArF light. As the resin of the component (A), it is preferred that the repeating unit is a resin composed only of repeating units of (meth)acrylic acid. In this case, any resin whose repeating unit is a repeating unit of methacrylic acid, a resin whose repeating unit is an acrylic repeating unit, and a repeating unit thereof consisting only of methacrylic acid repeating -30-200844664 unit and acrylic repeating unit may be used. Resin. Preferably, the resin contains an acrylic repeating unit in an amount of 50 mol% or less based on the total repeating unit, and more preferably the resin is an acid-decomposable group containing 20 to 5 mol%. Acrylic acid repeating unit, 20 to 50 mol% of (meth)acrylic acid repeating unit having a lactone structure, 5 to 30 mol% of (meth) having a trans- or cyano-substituted alicyclic hydrocarbon structure Acrylic repeating unit, and copolymer of ( to 20 mol% of other (meth)acrylic repeating units. The resin of the component (A) can be obtained by a conventional method (e.g., radical polymerization). Examples of commonly used synthetic methods include a polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating the resulting solution; and a solution containing the monomer species and the initiator is added dropwise to the heated solvent over 1 to 10 hours. The polymerization method is added dropwise. Among them, it is preferred to add the polymerization method dropwise. Examples of the reaction solvent include ethers (e.g., tetrahydrofuran, 1,4-dioxane and diisopropyl ether), ketones (e.g., methyl ethyl ketone and methyl isobutyl ketone), ester solvents (e.g., ethyl acetate), and decylamine solvents ( Such as dimethylformamide and dimethylacetamide), and the solvents used to dissolve the composition of the present invention (such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and cyclohexanone). . It is more preferably a polymerization using the same solvent used for the solvent of the photosensitive composition of the present invention. This suppresses the generation of particles during storage. The polymerization is preferably carried out in an inert gas atmosphere such as nitrogen and argon. The polymerization is started using a commercially available radical initiator such as an azo initiator or a peroxide as a polymerization initiator. As the radical initiator, it is preferably an azo initiator, more preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile and -31 - 200844664 dimethyl 2,2'-azobis(2-methylpropionate). The initiator may be added further or in portions if desired. After the end of the reaction, the reaction mixture is charged into a solvent, and the desired polymer is collected, for example, by a method for collecting a powder or a solid. The reaction concentration is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 1 Torr to 150 ° C, preferably from 30 to 120 ° C, more preferably from 6 Torr to 100 ° C °. The resin of the component (A) has preferably from 1,000 to 200,000, more preferably It is a weight average molecular weight of 3,000 to 20,000, preferably 5,000 to 15,000, as measured by GPC versus polystyrene. The weight average molecular weight is adjusted to 1, and the enthalpy to 200,000 can prevent deterioration of heat resistance or dry etching resistance while preventing degradation of developing power and deterioration of film formation properties due to thickening. The dispersibility (molecular weight distribution) is generally from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2. The smaller the molecular weight distribution, the better the resolution and the shape of the photoresist, and the photoresist pattern has smooth sidewalls and excellent roughness properties. The positive photosensitive composition for the exposure of KrF excimer laser light, electron beam, X-ray, or high energy beam (such as EUV) having a wavelength of 50 nm or shorter is used for the component (A). The resin of the component (A) preferably has a repeating unit represented by the formula (I) and a repeating unit having a hydroxystyrene structure. Examples of the repeating unit having a phenylene oxide-containing structure include o-, m- or p-hydroxystyrene and/or hydroxystyrene protected with an acid decomposable group. As the hydroxystyrene repeating unit protected by an acid-decomposable group, it is preferably 1-alkoxyethoxystyrene and tert-butylcarbonyloxystyrene. The resin may have a repeating unit represented by the formula (?) in addition to the repeating unit represented by the formula (I) and the repeating unit having a hydroxystyrene structure. -32- 200844664 The designated examples of the resin used in the present invention and having a repeating unit having a hydroxystyrene structure and a repeating unit represented by the formula (I) are shown below, but the invention is not limited thereto. In these specified examples, X a i represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

The amount of the resin of the component (A) in the entire solid of the positive photosensitive composition of the present invention is preferably from 50 to 99.9% by mass, more preferably from 60 to 99.0% by mass. In the present invention, the resin of the component (A) may be used singly or in combination. (B) Compound which generates an acid upon irradiation with light or radiation. The positive photosensitive composition of the present invention contains a compound which generates an acid upon irradiation with light like radiation or radiation (which may be referred to as an "acid generator" or "Component (B) -33- 200844664 compound"). Examples of compounds which generate an acid upon irradiation with light like radiation or radiation include diazonium salts, money salts, strontium salts, mineral salts, sulfhydrazine sulfonates, sulfonium sulfonates, and o-nitrobenzyl sulfonic acids. salt. Further, a compound obtained by introducing a group or a compound which generates an acid upon irradiation with light-like radiation or radiation into a polymer main chain or a side chain can be used. For example, it is described in U.S. Patent No. 3,849,137, German Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A - 62 - 69263, • JPA _ 6 3 1 4 6 0 3 8 , JPA - 6 3 - 1 6 3 4 5 2 , JPA - 6 2 - 1 5 3 8 5 3, and the compound of JP-A-63-1 46029. Further, a compound which produces an acid upon irradiation with light can also be used, for example, in U.S. Patent No. 3,779,778 and European Patent No. 126,712. As for the acid generator, it is preferably one having a non-nucleophilic anion. Preferred examples include a sulfonic acid anion, a carboxylic acid anion, a bis(alkylsulfonyl)guanamine anion, a sulfonium (alkylsulfonyl) methine anion, BF4·, PF6-, and SbF^. Among them, an organic anion having a carbon atom is preferred. Preferred examples of the organic anion include organic anions represented by the following formulas AN 1 to AN4. RC3SO2 RC3SO2

Rci-SOf Rci-COf RC4SO2-C © RC4SO2 RC5SO2 AN1 AN2 AN3 AN4 R c i represents an organic group. Examples of the organic group as RCl include a group. Preferred examples include a base group (which may be substituted) and an aryl group (which may be substituted), and a plurality of these groups -34-200844664 bonded groups (e.g., single bond, -Ο ·, -C Ο 2 -, - S -, - S Ο Connection.

Rdi represents a hydrogen atom or a hospital group, or may form a ring structure with an aryl group. As the organic group of RCl, it is preferred to improve the acidity of the alkyl group substituted with or a fluoromethyl group, and the fluorine atom or fluorine having a fluorine atom or a fluoroalkyl group to cause exposure. The Rq has 5 or more carbon atoms. The φ atom is preferably substituted by a hydrogen atom. More preferably, it is a hydrogen atom. Contains no perfluorinated with 5 or more carbon atoms. Low toxicity. It is also preferred that RCl is a group represented by the following formula. R〇7-Ax-Rc6

Rc6 represents a perfluoroalkyl group or a stretched phenyl group substituted with 3 to 5 fluoroalkyl groups.

Ax represents a bond group (preferably a single bond, _〇-, ®^-s〇2N(Rd1)., mw, ψ m

Rc? forms a ring structure). RC7 represents a hydrogen atom, a fluorine atom, a linear form, a noisy group (which may be substituted), or an aryl group (which may be substituted) (which may be substituted) preferably has no fluorine atom as RC3, and RC4 and Rc5 each represent an organic group. The organic groups of RC3, Rc4 and Rc5 are preferably as shown in the preferred examples. 3-, or -SO^Rch)-) RL-bonded alkyl group or benzene substituted at the 1-position by a fluorine atom alkyl group base. The acidity is increased, and when the sensitizer is present, the acid generator having at least one carbon atom greater than the fluoroalkyl group has a fluorine atom and/or 1 to 3 ^ -C02-, -S-, -S03-, an alkyl group, or Combine branches, single rings or multiple rings. Alkyl or aryl substituent. Similar to Rci's organic base -35- 200844664

Rc3 and Rc4 can be joined to form a ring. Examples of the group which forms RC3 and rC4 include an alkylene group and an extended aryl group, preferably a C2_4 perfluoroalkylene group. It is preferred to form Rc3 and Rc4 to form a ring because it increases the acidity of the acid produced by exposure and improves the sensitivity. As the acid generator used in the present invention, it is preferably a compound which produces an acid represented by the formula (BII). (Rb|)m people

\j/S〇3H

(Rb^n (BN) where in the formula (BII),

Rh represents a group having an electron attracting group,

Rb2 represents an organic group having no electron attracting group, m and η each represent an integer of 0 to 5, and the condition is m + n$5, and when m is 2 or more, a plurality of Rbi may be the same or different, and When it is 2 or more, a plurality of Rb2 may be the same or different. In the formula, m represents an integer of preferably from 1 to 5, more preferably an integer of from 2 to 5. The presence of an electron attracting group increases the acidity and sensitivity of the acid produced by light-like exposure. The group having an electron attracting group as Rbi is a group having at least one electron attracting group, and is preferably a group having 10 or less carbon atoms. The base with an electron attracting base can be an electron attracting body. The electron attracting group is preferably a fluorine atom, a fluoroalkyl group, a nitro group, an ester group or a cyano group, more preferably a fluorine atom. The organic group as the electron-free attracting group of Rb2 is preferably Cl_2(), more preferably 200844664 is C4-2〇, still more preferably Cf15 organic group. Preferable examples of the organic group include an alkyl group, an alkoxy group, an alkylthio group, a decyl group, a decyloxy group, a decylamino group, an alkylsulfonyloxy group, and an alkylsulfonylamino group. The organic group may have a hetero atom-bonding group in its alkyl chain. Preferred examples of the hetero atom-containing linkage group include -C(=0)0-, _C(=0)·, -S02-, _s〇3·, ·8〇2ν(Α2)_,-0-, and -S-. Two or more of these groups may be used in combination. In the above formula, Α2 is a hydrogen atom or an alkyl group (which may be substituted). When two or more groups are used in combination, it is preferably a combination of a hetero atom-free bonding group such as an alkyl group or an aryl group. These groups may have other substituents. Preferred examples of other substituents include a thiol group, a residue, a sulfur-brinding group, and a mercapto group. In the formula (ΒII), it is preferred that m represents an integer of 1 to 5, η represents an integer of 1 to 5, m + n^5, and Rh and Rb2 each have a C4_2() alkyl structure. The C4-2G alkyl structure suppresses the diffusion of acid generated by light-like exposure and improves the exposure latitude. In the formula (BII), each of Rh and Rb2 preferably has an alicyclic group. Particularly, the organic group having no electron-attracting group of Rb2 is preferably a group having an alicyclic group. The following is a specified example of the acid represented by the formula (BII). -37- 200844664

-38- 200844664

F F

SO3H 〇16Hg3〇

MeO S03H C12H25〇

Among the compounds which decompose and generate an acid upon irradiation with light like radiation or radiation, a compound represented by the following formulas (Zla) and (Zlla) is preferred. ^201 尺204一卜尺205 Xd-Zlla R202—ψ Xd- 泠203

Zla In the formula (Zla), R2 01, R2 02 and R2 03 each independently have an organic group. Χ(Γ represents an anion of an acid represented by the formula (BII). Specific examples of the organic group as R2()1, R2 0 2 and R203 include corresponding compounds (ZI-la), (ZI-2a) and (ZI) described later. The group of -3a) The organic group may be a compound having a plurality of structures represented by the formula (Zla). For example, the compound may have at least one of R201 to R2G3 to which the compound represented by the formula (Zla) is bonded to another a compound of the structure of at least one of R2〇1 to R2〇3 of the compound -39- 200844664 represented by the formula (Zla). The following compounds (ZI-la), (Zl_2a) and (ZI-3a) may be components ( A more preferred example of ZIa). The compound (ΖΙ-la) is an aryl mirror compound having an aryl group as at least one of r2 (u to R2〇3) in the formula (ZIa), that is, a compound having an aryl group as a cation In the aryl hydrazine compound, 'R2G1 to r2()3 may be an aryl group, or some of R201 to R2〇3 may be an aryl group, and the rest are a yard group. Examples of the Φ aryl fluorene compound include a triaryl mirror compound, a diarylalkyl hydrazine compound and an aryl dialkyl hydrazine compound. The aryl group of the aryl shovel compound is preferably an aryl group. For example, phenyl and naphthyl, or heteroaryl such as an anthracene residue and a pyrrole residue, more preferably a phenyl or an anthracene residue. When the aryl shovel compound has two or more aryl groups, these two The aryl group or groups may be the same or different. The aryl mirror compound has a hospital group (if necessary) preferably a linear, branched or cyclic Ci-H alkyl group, and examples thereof include a methyl group, an ethyl group, and a propyl group. , n-butyl, t-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl. The aryl or the aryl group of R2〇1 to R2〇3 may have an alkyl group (for example, ^115垸) a group, an aryl group (for example, C 6 · i 4 -group), an alkoxy group (for example, ci ^ 5 -oxy group), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent. The substituent is preferably linear or branched. Or a cyclic CM2 alkyl group, or a linear, branched or cyclic C^2 alkoxy group, most preferably a Cu alkyl group, or a Ci j alkoxy group. The substituent may be substituted for Rw to any of the three, or % may be substituted for all In the case of -40. 200844664 to R2G3, the substituents are preferably a preferred example of the radical cation at the position of the aryl group, including triphenylphosphonium cation. (which may be substituted), naphthyltetrahydrothiophene cation (which may be substituted), and phenyltetrahydrothiophene cation (which may be substituted). Next, the compound (ZI-2a) is described. The compound (ZI-2a) is A compound in which the caliper 2()1 to r2()3 of the formula (zia) each independently represents an aromatic ring-free organic group. The term "aromatic ring" as used herein includes even an aromatic ring containing a hetero atom. The aromatic ring-free organic group of i to R2〇3 has a usual from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms. R2〇i to R2〇3 are each independently and preferably represent a dean, 2·oxy; (: an end group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group, more preferably a linear shape, a branch or a ring shape) 2-oxoalkyl, or alkoxycarbonylmethyl, and most preferably linear or branched 2 · oxyalkyl. As R 2 (the alkyl group of U to R 2 0 3 may be any linear, branched or cyclic, ® and Preferably, it is linear or branched C ii decyl (such as methyl, ethyl, propyl, butyl, or pentyl), or cyclic C3.1G alkyl (such as cyclopentyl, cyclohexyl or norbornyl). The 2-oxyalkyl group as R2 (U to R2 0 3 may be linear, branched or cyclic, and preferably has a group of &gt; C = 0 at the 2-position of the alkyl group. As R2 (M to R203) The alkoxy group of the alkoxycarbonylmethyl group is preferably a Ci-5 alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, or pentyloxy). -41 - 200844664

Rw to R2〇3 may be further substituted with a halogen atom, an alkoxy group (e.g., Cl_5 alkoxy group), a hydroxyl group, a cyano group, or a nitro group. Two of R2〇i to R2〇3 may be bonded to form a ring, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a 醢fee bond, or a mineral group. Examples of the group in which the two of r2G1 to r2()3 are bonded include an alkylene group (e.g., a butyl group and a pentyl group). The compound (ZI-3) is a compound represented by the following formula (Z1-3 a) and having a phenylhydrazine sulfonium salt structure.

_Ry Xd- (Zl-3a) group, or halogen atom R6c and R7. Each represents a hydrogen atom or an alkyl group.

Rx and Ry each independently represent an alkyl group, a 2-oxyalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

At least any of Rlc to R5e, or Rx and Ry may be bonded to each other to form a ring structure' and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or a guanamine bond. Xd_ represents an anion of the acid represented by the formula (BII). The base of R 1 e to R 5 e may be any linear, branched or cyclical base such as an alkyl group. Preferred examples thereof include a linear or branched Ci 2 alkyl group (e.g., methyl, ethyl, linear or branched propyl, linear or branched butyl, and linear or branched pentyl), and cyclic C 3 -8 alkyl ( Such as cyclopentyl and cyclohexyl). As Rie to R5. The alkoxy group can be any linear, branched or cyclic -42 - 200844664 alkoxy, for example C 〇 oxy. Preferable examples thereof include a linear or branched C i -5 alkoxy group (such as a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, and a linear or branched pentyloxy group), and a ring shape. C3_8 alkoxy (such as cyclopentyloxy and cyclohexyloxy). It is preferably Ri. To R5. Either linear, branched or cyclic alkyl, or linear, branched or cyclic alkoxy. More preferably Ri. The carbon atom to R5e is from 2 to 15 . This improves the solubility in the solvent and prevents the generation of particles during storage. Xin is similar to Rl as an example of the base of Rx and Ry. To R5. The base of the hospital. Examples of the 2-oxyalkyl group include, for example, Rle to R5. The alkyl group shown &gt; C = 0 is shown at its 2-position. Examples of the alkoxycarbonylmethyl alkoxy group are similar to the alkoxy group of Rle to R5c. Examples of the group linking Rx and Ry include a butyl group and a pentyl group.

Rx and Ry are each preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more carbon atoms, still more preferably 8 or more carbon atoms. In the formula (Zlla), R2〇4 and R205 each independently represent an aryl group (which may be substituted) or an alkyl group (which may be substituted). The aryl group of R2〇4 or R2Q5 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The alkyl group as R2 0 or R2G5 is preferably any linear, branched or cyclic alkyl group. Preferred examples include linear or branched C1_1Q alkyl groups (e.g., methyl, ethyl, propyl, butyl, and pentyl), and cyclic. Alkyl groups (e.g., cyclopentyl, cyclohexyl and norbornyl). -43- 200844664 Examples of the substituent which R2〇4 or R2〇5 may have include an alkyl group (e.g., an alkyl group), an aryl group (e.g., a C6-15 aryl group), an alkoxy group (e.g., a Cl_15 alkoxy group), a halogen. Atom, meridine, and phenylthio. Further preferred examples of the compound which decomposes and generates an acid upon irradiation with light like radiation or radiation include compounds represented by the following formulas (Zllla) and (ZlVa).

〇 Ϊ

Xd—ΝΑ 7川 °

Zllla ZlVa

In the formula (Zllla) and (ZlVa),

Xd represents a monovalent group obtained by removing a hydrogen atom by an acid represented by the free form (BII). R2〇7 and R2〇8 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or an electron attracting group. RM7 is preferably a substituted or unsubstituted aryl group.

Rros is preferably an electron attracting group, more preferably a cyano group or a fluoroalkyl group. A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted extended aryl group. More preferably, the compound which decomposes and generates an acid upon irradiation with light like radiation or radiation is a compound represented by the formula (Zla) to (Zllla), and still more preferably a compound represented by the formula (Zla), and most preferably A compound represented by the formula (21-1昀). Next, a particularly preferred example of the component (B) is shown, but the invention is not limited thereto. 0 - 44 - 200844664

Examples of other preferred acid generators include, but are not limited to, the following compounds.

-45 - 200844664 (Q^|+〇F3SQ3- (Q^s+c2f5s〇3 (Qfs* C3F7so3- (Q^-s+〇4Fgs〇3-(z1) (z2) (z3) (Z4) (Q^ CeFiaSOf (Q^CsFnSOi (Q^+〇ιιΡ23〇〇σ (zs) (4) hm (z8) ^O^^4^03' 〇-〇^^4F0S〇i (-HQ^f -^S~¢9) (z1〇) (Z11) (212)

o

Ν·ο 言 C4F3 rc4F9s〇i (Q^s+ 3 (213⁄4 o

Oxi. o (z17) O O.SCF3o on2o o o (218) cP0^13 (z19&gt; OBu

C4H9 nr^ c4h9 C4F9S03· (z21) c4f9so3. (Z22) 0^.303- (223)

Of Ministry of Sand (224) F F F 9 Bu s+ -〇3s4-++s-o- ¢25) —S+. 2 "§-0-.2 production 45〇3- (4)) Bu 1, hanging 0 (Z27)

OBU

(z28) OBu

(〇r-〇4HK^ (Z30) -46- 200844664

〇5 s+ ©n’CF3〇 CF: (z31)

(Ot

C2F5 S+0N Language C2F5 (232)〇4ti+'-〇 Pi κι F F F O

〇|-c4f9 S 十 ΘΝ, 〇^S-C4F9 (z33) °

Θ N 〇^|-c3f7 -CFa (234) OBu

(z37) (z35) (z36) ΘΝ l O^S-CFa

_ C2F 5

〇=Ss〇 C2Fs

3 o order cf3 (241) O

〇-s44+l*°-〇KI) Ο 0=fs〇〇 :®υ^·Ό)ι+ — f F F 〇 (242)

The compound as the component (B) can be used singly or in combination. When two or more of them are used in combination, it is preferred to use a compound having a total number of atoms (except hydrogen atoms) which differs by 2 or more and which produces two kinds of organic acids. The content of the compound as the component (B) in the composition is preferably from 0.1 to 20% by mass, more preferably from 1 to 1% by mass, still more preferably from 3 to 8 by total solid content of the photoresist composition. % by mass, particularly preferably 4 to 7% by mass. (C) Compound insoluble in an alkali developer and having at least one of a fluorine atom and a ruthenium atom. The photosensitive composition of the present invention contains a water-insoluble developer and has a hydrophobicity of at least one of a fluorogenic-47-200844664 sub- and a ruthenium atom. Resin (C) (which may be referred to as "hydrophobic resin (HR)" or "resin (HR)") hereinafter. When a photosensitive film is formed from a composition containing a hydrophobic resin (HR), it can improve the following force of the immersion liquid because it concentrates the hydrophobic resin (HR) on the surface layer of the photosensitive film, and the photosensitive film is improved. The back tilt contact angle of the surface with water as the impregnation medium. As the hydrophobic resin (HR), any resin which can improve the post-contact angle of the surface can be used, but a resin having at least one of a fluorine atom and a ruthenium atom is preferable. The back contact angle of the photosensitive film formed using the photosensitive composition of the present invention is preferably from 60 to 90. More preferably 70° or more. It may be added with a hydrophobic resin (HR) and the tentacles after the photosensitive film are adjusted to the above range as desired. It is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the photosensitive composition. The term "backward contact angle" as defined herein means the angle of contact of the water droplets measured by the expansion/contraction method. More specifically, it can be measured using a fully automatic contact angle meter ("DM700", trade name; product of Kyowa Interface Science). After a droplet of 36 μl was formed on the positive resist composition prepared by the syringe on the crucible wafer, the droplet was aspirated at a rate of 6 μl/sec. The contact angle which became stable during the suction was taken as the backward tilt contact angle. As described above, the hydrophobic resin (HR) is concentrated on the interface intensively, but unlike the surfactant (E), it does not necessarily have a hydrophilic group in the molecule and promotes uniform mixing of the polar/nonpolar substance. The resin (HR) is insoluble in the alkali developer. The term "insoluble in alkali developer" as used herein means the cumulative amount of the resin film in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C with respect to the cumulative amount of 3 seconds after the start of development from -48 to 200844664. The amount is 20 nm or less. The resin is preferably an alkali-free group or a group having enhanced solubility in an alkali developer. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonylamino group, a sulfonyl fluorenylene group, or an alkylsulfonyl group (alkylcarbonyl group). Methyl, (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl) a group of a methyl group, a bis(alkylsulfonyl) fluorenylene group, a Φ s(alkylcarbonyl)methylene group, and a cis (alkylsulfonyl)methylene group. Examples of the group having an enhanced solubility in the alkali developer include a group having a lactone structure, an acid anhydride, and an acid sulfonium imide group. The specified examples include the lactone structure shown by the above resin (A). The resin (HR) is preferably stabilized in an acid. The term "stabilized in acid" means that the resin does not contain a repeating unit which is decomposed by the action of an acid and becomes soluble in an alkali developer, and which does not decompose even in the presence of an acid produced by a photoacid generator. Examples of the acid-decomposable group are similar to those shown above for the resin (A). The fluorine atom or the ruthenium atom of the resin (HR) may be present in the main chain of the resin or may be substituted with its side chain. The resin (HR) is preferably a resin having a fluorine-containing partial structure having a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group, or a fluorine-containing aryl group. The fluorine-containing alkyl group (preferably, more preferably a C4-alkyl group) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It may have other substituents. -49 - 200844664 A fluorine-containing cycloalkyl group is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom. It may further have other substituents. The fluorine-containing aryl group is an aryl group (e.g., phenyl or naphthyl group) in which at least one hydrogen atom is substituted with a fluorine atom. It may further have other substituents. The fluorine-containing alkyl group, the fluorine-containing cycloalkyl group and the fluorine-containing aryl group are shown below, but the invention is not limited thereto.

Ree

Re4

Res· ^63

Re2 (F3)

R67OH ^68 (F4) In the formulae (F2) to (F4), R5 7 to R68 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and the condition is at least one of R57 to R61 and at least one of R62 to R64. And at least one of R65 to R68 each represents an alkyl group (preferably an alkyl group) in which a fluorine atom or at least one hydrogen atom thereof is substituted with a fluorine atom, which is preferably a chemical group to a group The fluorine atom. R62, R63 and R68 each preferably represent an alkyl group (preferably a C i alkyl group) in which at least one hydrogen atom is substituted by a fluorine atom, more preferably a Cl-4 perfluoroalkyl group. R62 and R63 may be used. The ring-forming examples of the group represented by the formula (F2) include p-fluorophenyl group, pentafluorophenyl group, and 3,5-bis(trifluoromethyl)phenyl group, which is represented by the formula (F3). Specific examples of the group include trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, heptafluoroisopropyl, and hexa-50-200844664 fluoro(2-methyl) Propyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluorobutanyl, perfluoroisopentyl, perfluorooctyl, perfluoro(trimethyl)hexyl, 2,2,3 , 3-tetrafluorocyclobutyl, and perfluoro Hexyl. Among them, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-t-butyl, and perfluoroisopentyl are preferred. More preferred are hexafluoroisopropyl and heptafluoroisopropyl. Specific examples of the group represented by the formula (F4) include -C(CF3)2OH, -C(C2F5)2〇H, -C(CF3)(CH3) 〇H, and -CH(CF3)〇H, preferably -C(CF3)2〇H 〇 The fluorine-containing resin as the resin (C) preferably has at least one selected from the group consisting of the following formula (1-1); (1-2) and (1-3) repeating units of the fluorine-containing repeating unit. R-| R2 R4 ^5钧一Η Pity r6 r7 (Μ) (1-2)

In the formulas (1-1) to (1-3),

Ri represents a hydrogen atom or an alkyl group, R2 represents a fluorine-based group, R3 represents a hydrogen atom or a monovalent organic group, and R4 to R? each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkoxy group, and the condition is R4 to At least one of R7 represents a fluorine atom, and R5 or r6 and r7 may be bonded to form a ring,

Rs represents a hydrogen atom, a fluorine atom or a monovalent organic group, -51 - 200844664

Rf represents a fluorine atom or a monovalent organic group having a fluorine atom, L represents a single bond or a divalent bond group, Q represents an alicyclic structure, and k is an integer of 0 to 3. In the formula (1-1), the alkyl group of Ri is preferably a linear or branched Cl-5 alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a second butyl group. , pentyl, isopentyl, neopentyl, and third amyl. R1 is preferably a hydrogen atom. The fluorine-based group of R 2 is, for example, the above-mentioned linear or branched c i _ 5 fluorenyl group substituted with at least one fluorine atom, preferably a perfluoro yard. R2 is preferably a trifluoromethyl group. Examples of the monovalent organic group of the rule 3 include an alkyl group (preferably a CbH 1 fluorenyl group), a fluorenyl group (preferably a C3-15 ring-based group), an aryl group (preferably a C 5 aryl group). , a fluoroaryl group (preferably a C6-15 fluoroaryl group), a fluorenyl group (preferably a Cm fluorenyl group), and an alkoxycarbonyl hydrazine group preferably a group of a (a) alkoxycarbonyl group; and directly or via The divalent linkage unit combines two or more of the above 10 groups. Examples of the divalent linking group of L include a group selected from the group consisting of a stretching group, an aryl group, an ether group, a thioether group, a carbonyl group, an ester group, a decyl group, a urethane group, and a ureido group; Two or more of these groups are used in combination. In the formula (1-2), examples of the alkyl group of R4 to R7 are similar to the alkyl group and the fluoroalkyl group represented by the formulas Ri and R2. The alkoxy group of R4 to R7 is preferably an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a n-butoxy group, or an alkoxy group of -52-200844664 by at least one fluorine atom. Substituted fluoroalkoxy. An example of the organic group of R8 in the formula (1-3) is similar to that shown by r3 in the formula (--). Examples of the monovalent organic group having a fluorine atom as Rf include a linear or branched alkyl group (preferably Cl_1() alkyl group) substituted with at least one fluorine atom, and a cycloalkyl group substituted with at least one fluorine atom (preferably). For c3_10 ring )). Examples of the divalent linking group of L include a group selected from the group consisting of a stretching group, an aryl group, an ether group, a thioether group, a carbonyl group, an ester group, a decyl group, a urethane group, and a ureido group; Two or more of these groups are used in combination. The alicyclic structure of Q is, for example, one of the following structures, but the invention is not limited thereto. In this structure, P is an integer from 〇 to 3.

The formula (1-1) is preferably represented by any one of the following formulae (2-1) to (2-3).

Ri cf3 wins C a c + Η Λ R1 cf3 a ό &quot;·)—

In the formulas (2-1) to (2-3),

Ri represents a hydrogen atom or an alkyl group, and -53- 200844664 R3 represents a hydrogen atom or a monovalent organic group. 1 and ^ in the formulae (2-1) to (2-3) have the same meanings as described in the formula (1-1). The following are designated examples of fluorine-containing repeating units. In this structure: represents a hydrogen atom, -CH3, -F, or -CF3, and X2 represents -F or

Ri and R3 ζ, X! -C F 3.

-54- 200844664

The resin (HR) is also preferably a resin having an alkyl fluorenyl structure (preferably a trialkyl decyl group) or a cyclic siloxane structure as a fluorene-containing partial structure. -55 - 200844664 Alkyl fluorenyl structure or cyclic oxane structure means that the β β 1 1 tongue is represented by the following formula (CS-1) to (CS-3):

Ls R12 -〒一 RU R13 R16-s T〇^srR^ R18 $ ,R20h'sA士之J) (CS -1) R17 (CS - 2) ^26 R25 (CS-3) 〇&quot;SUR24

In the formulae (CS-1) to (CS-3), R12 to R26 each independently represent a linear or branched alkyl group (preferably a Ci. 20 alkyl group) or a cycloalkyl group (preferably a c3-2G alkyl group). ). Each of L3 to L5 represents a single bond or a divalent bond. Examples of the divalent linking group include a group selected from an alkyl group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, a decylamino group, a urethane group, a ureido group, and a combination thereof. Or more of these bases. η represents an integer of 1 to 5. The resin (HR) preferably has a hydrazine-containing repeating unit represented by the following formula (CI) and/or a hydrazine-containing repeating unit represented by the following formula (C II) as a hydrazine-containing repeating unit.

R〇2 (CII) In the formulas (CI) and (CII),

Lc represents a single bond or a divalent bond, -56- 200844664

Rci each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxycarbonyl group,

Rc2 represents a monovalent organic group having at least one deuterium atom,

Re3 represents a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group,

Qc represents an alicyclic structure, and kc is an integer from 〇 to 3. In the formula (CI), the alkyl group of RCl is preferably a linear or branched Cu alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, di-butyl, Pentyl, isopentyl, neopentyl, or a third amyl group.

The cycloalkyl group of Rq is preferably a c3 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group or a cyclopentyl group. The alkoxy group is preferably a C5 alkoxy group such as a methoxy group, an ethoxy group, a n-propoxy group or an isopropoxy group. The alkoxycarbonyl group is preferably a &lt;^-30 alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, or a cyclohexyloxy group. Alkylcarbonyl. • The above alkyl group, cycloalkyl group, alkoxy group or alkoxycarbonyl group may have a substituent. Examples of the substituent which the alkyl group, the cycloalkyl group, the alkoxy group or the alkoxycarbonyl group may have include a halogen atom and a hydroxyl group. Ri may have a deuterium atom in its substituent. I is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Examples of the divalent linking group of L c include an alkylene group, a cycloalkylene group, an extended aryl group, an ester group, a sulfonic acid group, an ether group, a ketone group, a sulfonyl group, and a combination of two or more. These bases are planted. -57- 200844664

Lc is preferably a single bond or an ester group (_C (=0)-0-).

Rc2 has a monovalent organic group having at least one deuterium atom. A linear or branched Cioo alkyl group having at least one deuterium atom, or a linear or branched C3-3-oxocycloalkyl group having a deuterium atom.

Examples of the linear or branched Cl_3() alkyl group of Rc2 include methyl n-propyl, isopropyl, n-butyl, isobutyl, t-butylpentyl, neopentyl, tert-amyl, hexyl, heptyl. , octyl, undecyl, dodecyl, tridecyl, tetradecyl Φ, hexadeca, heptadecyl, octadecyl, pentadecanyl. Examples of the C3-3()cycloalkyl group of RC2 include a cyclopropylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclodecyl group, a norbornyl group, or a fluorenyl group.

The alkyl group or the cycloalkyl group of Rh may be further substituted by a halogen atom or the like, or the position at which a plurality of divalent bonds may be contained in the chain is not particularly limited. ® The following are examples of the specified repeating units. In the formula, an atom, -CH3, -F, or -CF3. It preferably has at least one group, ethyl group, pentyl group, iso-, decyl group, fluorenyl group, pentadecyl group, eicosyl group, cyclopentyl group, adamantyl group, (preferably a fluorine group. Originally, X 1 represents hydrogen -58- 200844664

The resin (HR) may further have a repeating unit represented by the following formula (I 11). Ten ch2—

U

I

FU (I Ϊ I) In the formula (III), r4 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group or a cycloalkenyl group, and 16 represents a single bond or a divalent bond group. The r4 alkyl group in the formula (in) is preferably a linear or branched c3_2() alkyl group. The cycloalkyl group is preferably a c3_2() cycloalkyl group. -59- 200844664 The suspicion base is preferably a C3-20 suspicion. The divalent linking group of L0 is preferably an alkylene group (preferably a Ci5 alkyl group) or a pendant oxy group. When the resin (HR) has a fluorine atom, the fluorine atom content is preferably from 5 to 80% by weight, more preferably from 1 to 8 % by mass, based on the molecular weight of the resin (HR). The content of the fluorine-containing repeating unit in the resin (HR) is preferably from 1 to 1% by mass, more preferably from 30 to 1% by mass. When the resin (HR) has a ruthenium atom, the ruthenium atom content is preferably from 5 to 80% by mass, more preferably from 1 Torr to 80% by mass, based on the singular molecular weight of the resin (HR). The ruthenium-containing repeating unit is preferably from 10 to 1% by mass of the resin (HR), more preferably from 30 to 100% by mass. The resin (HR) preferably has a weight average molecular weight of preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 15,000, relative to the polystyrene standard. Of course, similar to the acid-decomposable resin (A), the resin (HR) has as small an impurity as possible (such as a metal), and it contains 0 to 1% by mass, more preferably 0 to 5 % by mass, still more preferably 〇 A residual monomer or oligomer component in an amount of up to 1% by mass. This resin provides a photoresist that does not undergo a time-dependent change in the foreign matter or sensitivity of the liquid. From the viewpoints of resolution, photoresist profile, sidewall of the photoresist pattern, and roughness, it has a molecular weight distribution in the range of preferably from 1 to 5, more preferably from 1 to 3, still more preferably from 1 to 2. (Mw/Mn, also known as "dispersibility"). As the resin (HR), a commercially available product may be used, or the resin may be in a known manner (for example, radical polymerization y synthesis. Example of a common synthetic method - 60-200844664 includes dissolving a monomer species and an initiator in a solvent and The polymerization solution is heated while the resulting solution is heated; and the solution containing the monomer species and the initiator is added dropwise to the polymerization solvent by dropwise addition to the heated solvent over 1 to 1 hour, wherein a polymerization method is preferably added dropwise. Examples of the reaction solvent include ethers (e.g., tetrahydrofuran, 1,4-dibenzopyrene and diisopropyl ether), ketones (e.g., methyl ethyl ketone and methyl isobutyl ketone), vinegar solvents (e.g., ethyl acetate), and decylamine solvents ( For example, dimethylformamide and dimethyletheneamine, and a solvent (such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and cyclohexanone) for dissolving the composition of the present invention described later. Preferably, it is a polymerization using the same solvent used for the solvent of the photosensitive composition of the present invention. This inhibits the generation of particles during storage. The polymerization is preferably carried out in an inert gas atmosphere such as nitrogen and argon. Use commercially available from A radical initiator (such as an azo initiator or a peroxide) is started as a polymerization initiator. As for the radical initiator, it is preferably an azo initiator, more preferably an azo having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl 2,2'-azobis(2-methylpropionate). 5 to 50% by mass, preferably 30 to 50% by mass. The reaction temperature is usually from 10 to 150 ° C, preferably from 30 to 120 ° C, more preferably from 60 to 100 ° C. After completion of the reaction, the reaction product is cooled to room temperature and purified. The purification may be carried out by a conventional method. Examples include a purification method in a solution state, such as a solution of residual monomer or oligomer component by water washing or a combination of a suitable solvent. a liquid extraction method, and an ultrafiltration for extracting and removing a component having a molecular weight lower than a specified ruthenium, and a method in a solid state, such as by adding a resin solution dropwise to a poor solvent and causing the resin to coalesce in a poor solvent Re-precipitation method for removing residual monomers - 6 1 - 200844664, etc., and clearing with poor solvent a method of filtering a resin, for example, a reaction solution in which a volume is 10 times or less by volume of the resin, preferably 10 to 5 times, a solvent in which a resin is poorly soluble or insoluble (poor solvent), And precipitated into a solid. Any solvent may be used for precipitating or reprecipitating the solvent from the polymer solution (precipitation or reprecipitation solvent) as long as it is a poor solvent of the polymer. Depending on the type of the polymer, the solvent may be selected as desired. a hydrocarbon, a halogenated hydrocarbon, a nitro compound, an ether, a ketone, an ester, a carbonate, an alcohol, a carboxylic acid, water, and a mixed solvent thereof. φ a solvent containing at least one alcohol (particularly methanol or the like) or water Preferably, the solvent is precipitated or reprecipitated. Although the amount of the precipitating or reprecipitating solvent can be determined as desired, it is usually 100 to 100,000 parts by mass, preferably 100 parts by mass of the polymer solution, as determined. 200 to 2000 parts by mass, more preferably 300 to 1,000 parts by mass. Although the temperature during precipitation or reprecipitation takes into account the efficiency and operating force, as desired, it is typically from 50 to 50. (:, preferably near room temperature (for example, about 20 to 35 ° C). The precipitation or reprecipitation operation can be carried out by a known method such as a batch method or a continuous method using a mixing vessel such as a stirring tank. The polymer obtained by precipitation or reprecipitation is usually subjected to conventional solid-liquid separation, such as filtration or centrifugation, and is used after drying. The filtration is carried out using an anti-solvent filter material, preferably under pressure. The vehicle drying is carried out at normal or low pressure (preferably at low pressure) at a temperature of about 30 to 100 ° C, preferably 30 to 5 ° C. Once the resin is precipitated and separated, The resin can then be re-dissolved in Solvent-62-200844664 and contacted with a solvent in which the resin is poorly soluble or insoluble. More specifically, the method can include contacting the polymer with the polymer after the end of the free radical polymerization reaction. Precipitating the resin with a solvent dissolved or insoluble (step a), separating the resin from the solution (step b), and re-dissolving the resin in the solvent to prepare a resin solution A (step c), bringing the resin solution A into contact with a volume smaller than the tree. 1 of the volume of the fat solution A 0 times (preferably not more than 5 times) of a solvent in which a resin is poorly soluble or insoluble to precipitate a resin solid (step d), and then the step of separating the thus precipitated resin (step e). φ The following is a resin ( A designated example of C). The molar ratio of the repeating unit of each resin (corresponding to the molar ratio of the repeating unit from left to right shown in the specified examples), the weight average molecular weight, and the dispersibility are shown in the following table. -63- 200844664 • (ch2^ ^Hi,^^HlJ^ 邮·!) (HR-2) (HR-3) (HR4&gt; (HR-5) W^B- ^ CH, ^ If you call 旮和旮和芬和·ΧΪ7 0^0 fCH2&lt;-^ 0^0 0^*S&gt; C^SO^o

1- ^ 〇r^P, Ο V $ V V (HR*6) (HR-7) I m^} ^

Drinking H \ ^ φ \ 〇 ^R-10) (HR-H) 〇«?42) ρ?·ΐ3)

^R-42) -64- 200844664

Table 1 Resin composition Mw Mw/Mn HR-1 50/50 8800 2.1 HR-2 50/50 5200 1.8 HR-3 50/50 4800 1.9 HR-4 50/50 6300 1.9 HR-5 100 5500 2.0 HR-6 50 /50 7500 1.9 HR-7 70/30 10200 2.2 HR-8 40/60 15000 2.2 HR-9 80/20 11000 2.2 HR-10 50/50 8000 2.2 HR-11 50/50 7600 2.0 HR-52 50/50 12000 2.0 HR-13 20/80 6500 1.8 HR-14 100 6500 1.2 HR-15 100 6000 1.6 HR-16 100 2000 1.6 HR-17 50/50 6000 1.7 HR-18 50/50 8800 1.9 HR-19 50/50 7800 2.0 HR-20 80/20 8000 1.8 HR-21 30/70 7000 1.7 HR-22 50/50 6500 1.6 HR-23 50/50 6500 1.6 HR-24 50/50 9000 1.8 HR-25 100 10000 1.6 HR- 26 70/30 8000 2.0 HR-27 10/90 8000 1.8 HR-28 30/30/40 9000 2,0 HR-29 50/50 6000 1.4 HR-30 50/50 5500 1.5 HR-31 50/50 4800 1.8 HR-32 50/50 10600 1.9 HR-33 50/50 8000 1.5 HR-34 20/80 7500 1.8 HR-35 50/50 6200 1.6 HR-36 60/40 16000 1.8 HR-37 80/20 10200 1.8 HR- 38 50/50 12000 2.6 HR-39 50/50 6000 1.4 HR-40 50/50 4500 1.4 HR-41 100 2300 2.6 HR-42 100 15000 2.1 -65- 200844664 To prevent direct contact of the photoresist film with the impregnation Body of immersion liquid sparingly soluble film (hereinafter, this film may be referred to as "topcoat") may be formed between the resist film formed of the resist composition of the present invention is to make the immersion liquid. The functions required for the topcoat include the application of the upper layer of the photoresist, the transparency to the radiation (especially the wavelength of 93 nm), and the poor solubility in the immersion liquid. The topcoat is preferably not mixed with the photoresist and uniformly applied to the photoresist surface. From the viewpoint of transparency of 193 nm, the top coat is preferably an aromatic-free polymer. Designated examples include hydrocarbon polymers, acrylate polymers, poly(methyl φ acrylate), poly(acrylic acid), poly(vinyl ether), ruthenium containing polymers, and fluoropolymers. The above hydrophobic resin (HR) is also suitable as a top coat. Since the impurities are released from the topcoat to the contaminated optical lens in the immersion liquid, the residual monomer component of the polymer in the topcoat is preferably as small as possible. In order to remove the topcoat, a developer can be used. Alternatively, the topcoat can be removed using a remover separately. The remover is preferably a solvent which is less permeable to the photosensitive film. Removal by alkali developer is preferred because it allows the topcoat removal step to be simultaneous with the development step of the photosensitive film. Although it is preferable to remove the surface with an alkali developer ® paint is preferably acidic, in order to prevent intermixing with the photosensitive film, the top coat may be neutral or alkaline. The smaller the refractive index between the topcoat and the immersion liquid, the better the resolution. When an ArF excimer laser (wavelength: 193 nm) is used as the impregnating liquid, the ArF immersion exposure top coat preferably has a refractive index close to that of the immersion liquid. In order to obtain a near-impregnation liquid, the top coat is preferably a fluorine-containing atom therein. The topcoat is preferably thin from the viewpoint of transparency and refractive index. Preferably, the topcoat is not intermixed with the photoresist or the impregnating liquid. -66- 200844664 From this point of view, when the immersion liquid is water, the solvent used for the top coat is a solvent which is hardly soluble in the photosensitive composition and is water-insoluble. When the liquid is an organic solvent, the topcoat may be water soluble or water insoluble. (D) Solvent The above components are dissolved in a predetermined agent in the photosensitive composition of the present invention. Its general organic solvent acts as a solvent. Examples of the solvent include dioxane, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, φ alcohol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and B. Diethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl methyl ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl propyl propionate, methyl pyruvate Ethyl pyruvate, propyl pyruvate, dimethylformamide, dimethyl sulfoxide, hydrazine-methylpyrrolidone, and tetrapyran. Although the organic solvent may be used singly or in combination in the present invention, it is a mixed solvent using a solvent containing two or more kinds of different functional groups. Not only can the solubility of the material be improved, but also the grain production over time can be formed to form a good pattern shape. . The functional group contained in the solvent includes an ester group, a hydroxyl group, a ketone group, and a carbonate group. As the solvent having a different functional group, a mixed solvent of (S1) to (S5) shown below is preferred. (S 1 ) A solvent (S 2 ) in which a hydroxyl group-containing solvent and a hydroxyl group-free solvent have been mixed, wherein a solvent having an ester structure and a mixed solvent having a ketone structure agent have been mixed. (S3) A solvent in which an ester structure has been mixed with a solvent which is preferably impregnated with a lactone is preferably chloroethylene glycol benzene, ethoxy hydrazine or hydrazine-hydrofuran. It is a mixed solvent of the solvent of -67- 200844664. (S 4) A solvent having an ester structure, a solvent having a lactone structure, and a mixed solvent with a hydroxyl group-containing solvent are mixed therein. (S5) A solvent having an ester structure, a solvent having a carbonate structure, and a mixed solvent with a hydroxyl group-containing solvent have been mixed therein. The use of this mixed solvent can reduce the generation of particles during storage of the photoresist solution and prevent the occurrence of defects during coating. Examples of the hydroxyl group-containing solvent 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 them, propylene glycol monomethyl ether and ethyl lactate are particularly preferred. Examples of the hydroxy-free solvent include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, hydrazine, hydrazine. - dimethyl acetamide, and dimethyl hydrazine. Among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are preferred, and propylene glycol monomethyl ether acetate is preferred. Ester, ethyl ethoxypropionate, 2-heptanone, and cyclohexanone. Examples of the solvent having a ketone structure include cyclohexanone and 2-heptanone. Among them, cyclohexanone is preferred. Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and butyl acetate. Among them, propylene glycol monomethyl ether acetate is preferred. Examples of the solvent having a lactone structure include γ-butyrolactone. Examples of the solvent having a carbonic acid structure include propylene carbonate and ethyl carbonate. Among them, preferred is propyl carbonate. Further, the photoresist composition of the present invention is particularly preferably a mixed solvent containing at least one of propylene glycol monomethyl ether acetate, 2-heptanone and γ-butyrolactone. The solvent-containing solvent and the non-hydroxyl solvent are mixed at a ratio (mass ratio) of from 1/99 to 99/1, preferably from 10/90 to 90/10, still more preferably from 20/80 to 60/40. From the viewpoint of uniform coating, it is particularly preferably a mixed solvent containing 50% by mass or more of a non-hydroxyl solvent. The solvent having an ester structure and the solvent having a ketone structure are in a ratio of from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 40/60 to 80/20 (mass ratio). mixing. From the viewpoint of uniform coating, it is particularly preferably a mixed solvent containing 50% by mass or more of a solvent having an ester structure. The solvent having an ester structure and the solvent having a lactone structure are mixed at a ratio of 70/30 to 99/1, preferably 80/20 to 99/1, more preferably 90/10 to 99/1 (mass ratio). . From the viewpoint of uniform coating, it is particularly preferably a mixed solvent containing a solvent having a % or more by mass of an ester structure. In the case of mixing a solvent having an ester structure, a solvent having a lactone structure, and a solvent containing a hydroxyl group, the mixed solvent preferably contains 30 to 80% by weight of a solvent having an ester structure, and 1 to 20% by weight has A solvent of a lactone structure, and a hydroxyl group-containing solvent of 10 to 60% by weight. In the case of mixing a solvent having an ester structure, a solvent having a carbonic acid structure, and a solvent having a hydroxyl group, the mixed solvent is preferably a solvent having an ester structure of from 30 to 80% by weight, and from 1 to 20% by weight. A solvent having a carbonic acid structure and 10 to 60% by weight of a perbasic solvent. (Ε) a basic compound. It is preferred that the positive photosensitive composition of the present invention contains a preferred inductive compound-69-200844664 (E) to reduce the change in performance from exposure to heating over time, or to control exposure. The acid produced when it diffuses in the film. The basic compound includes a nitrogen-containing basic compound and a key salt compound. Preferable examples of the structure of the nitrogen-containing basic compound include compounds having a partial structure represented by the following formulas (A) to (E).

Partial

In the above formula, R2 5 G, R251 and R2 5 2 each independently represent a hydrogen atom or Cu. An alkyl group, a C3_2()cycloalkyl group, or a C6-2〇aryl group, or R25Q and R251 may be bonded to form a ring. These groups may have a substituent. Preferred examples of the alkyl group or cycloalkyl group having a substituent each include a Chw aminoalkyl group and a Ci-20 hydroxyalkyl group, and a C3_2G aminoalkylcycloalkyl group and a C3_2()hydroxycycloalkyl group. These groups may further contain an oxygen atom, a sulfur atom or a nitrogen atom in their alkyl chain. In the above formula, R253, R254, R255, and R256 each independently represent a mountain-6 alkyl group or a C3_6 cycloalkyl group. Preferable examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperidine, aminomorpholine, aminoalkylmorpholine, and piperidine, and they may have a substituent. More preferred examples of the compound include a compound having an imidazole structure, a diazobicyclic structure, a hydrazine hydroxide salt structure, a carboxylate salt structure, a trialkylamine knot-70-200844664 structure, an aniline structure, or a pyridine structure, having a hydroxyl group and An alkylamine derivative of an ether bond, and an aniline derivative having a hydroxyl group and a 7 or ether bond. Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazobicyclic structure include 1,4·diazabicyclo[2·2·2]octane, 1, diazabicyclo[4.3.0]non-5-ene and 1,8-diaza Bicyclo [5.4·0]~|--carbon-7-ene. Examples of the compound having a KOH salt structure include triaryl hydrazine hydroxide, benzamidine hydroxide, and cesium hydroxide having a 2-oxyalkyl group. Specific examples thereof include triphenylsulfonium hydroxide, hydrazine hydroxide (t-butylphenyl)phosphonium, bis(t-butylphenyl)phosphonium hydroxide, benzamidine thiophene hydroxide, and gas oxidation 2 - Oxypropyl thiophene salt. Examples of the compound having a carboxylate salt structure include a ruthenium hydroxide salt structure in which an anion portion thereof has been converted into a carboxylic acid group (for example, an acetate group, adamantane-1-carboxylic acid group and a perfluoroalkylcarboxylic acid group) Compound. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline and hydrazine, hydrazine-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, methoxy(methoxyethoxyethyl)amine, and hydrazine-phenyldiethanolamine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include anthracene, bis-bis(hydroxyethyl)aniline. It is particularly preferred that the photoresist composition of the present invention contains at least one of 2,6-diisopropylaniline and tetrabutylammonium hydroxide. These basic compounds can be used singly or in combination. The basic compound is used in an amount of from 0.1 to 10% by mass, preferably from 0 to 〇1 to 5% by mass, based on the solid content of the positive photosensitive composition. In order to obtain a sufficient effect of adding 200844664, the amount is preferably 0.0101% by mass or more, which is not more than 1% by mass from the viewpoint of the sensitivity of the unexposed region and the developing property. (F) Surfactant The positive photosensitive composition of the present invention preferably contains a surfactant. Preferably, the surfactant comprises one or two or more of a fluorine-containing and/or cerium surfactant (fluorine-containing surfactant, cerium-containing surfactant, and a fluorine-containing and cerium-containing surfactant). Due to the presence of a fluorine-containing and/or rhodium-based surfactant, the resulting positive-type photosensitive composition can be used with good sensitivity when a light source having a wavelength of 250 nm or φ is used, particularly a light source of 220 nm or less, for exposure. And the resolution provides a photoresist pattern that exhibits good adhesion and less development defects. Examples of the fluorine-containing and/or antimony surfactant include those described in JP-A-62-3 6663, JP-A-6 1 -226746, JP·A-6 1 -226745, J PA- 6 2 - 1 7 0 9 5 0 , J PA- 6 3 - 3 4 5 4 0 , JP-A-7-23 0 165 , JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2000-277862, and US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296, 3 3 0, 5,43,098, 5,576,143, 5,294, 5 1 1 and 5,824,45 1 Active agent. The following commercially available surfactants can also be used directly. Examples of commercially available surfactants useful herein include fluorosurfactants and hydrazine-containing surfactants such as "Eftop EF301" and "Eftop EF3 03" (each brand name; product of Shin-Akita Kasei)," Florad FC43 0” and “FI o rad 431” (each brand name; product of Sumitomo 3M), “Megaface F 1 7 1,,,” Megaface F 1 7 3,,,” Megaface F 1 7 6,, ''Megaface F 1 89' and ''Megaface R08' (each brand name; Dainippon -72- 200844664

Ink &amp; Chemicals products)," Surflon S - 3 8 2,,,,,Sur f 1 ο η SC 1 0 1''," Surflon 10 2" ' ''Surflon 1 0 3,,,,' Surflon 104,,, "Surflon 105", and 'Surflon 106" (each brand name; product of Asahi Glass), and "Troysol S-366" (trade name; product of Troy Corporation). A polyoxyalkylene polymer "KP-341" (trade name; product of Shin-Etsu Chemical) can also be used as the sand-containing surfactant. In addition to the above-mentioned known surfactants, it is possible to use a fluoroaliphatic-based polymer (derived from a short-chain polymerization method (also known as a short-chain polymer method) or a φ-oligomerization method (also known as an oligomer method). a surfactant of a fluoroaliphatic compound produced. This fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-9099 No. 1 patent. As the fluorine-containing aliphatic polymer, it is preferably a copolymer of a fluorine-containing aliphatic monomer, poly(oxyalkylene)acrylate, and/or poly(oxyalkylene)methacrylate. In this copolymer, these monomers may be irregularly distributed or block copolymerized. Examples of poly(oxyalkylene) include poly(oxyethyl), poly(oxypropyl) and poly(oxybutylene). It may also be a unit having an alkyl group having a different chain length in the same chain, such as block bond polycondensation (oxyethyl, propyl and oxyethyl) and block bonding (oxygen) Ethyl and oxygen extended propyl). Further, the copolymer of the fluoroaliphatic monomer and the poly(oxyalkylene) acrylate and/or the poly(oxyalkylene)methacrylate may be not only a binary copolymer but also a total of Polymerizing a ternary or higher copolymer having two or more different fluoroaliphatic monomers and two or more different poly(oxyalkylene) acrylates (or methacrylates) . Commercials. Examples of surfactants include "Megaface F 178,, -73- 200844664 "Megaface F-470", 55 Megaface F-473", ''Megaface F-475', "Megaface F-476", and "Megaface F-472" (each brand name; product of Dainippon Ink &amp; Chemicals). Further examples include C6F13 based acrylate (or methacrylate) and poly(oxyalkylene) acrylate (or methyl) Acrylate) copolymer containing C6F13 based acrylate (or methacrylate), poly(oxyethylidene) acrylate (or methacrylate) and poly(oxypropyl) acrylate (or methyl) Copolymer of acrylate, containing c8F17-based acrylate (or methacrylate) • copolymer with poly(oxyalkylene) acrylate (or methacrylate), and c8F17-based acrylate (or a copolymer of poly(oxyethylidene) acrylate (or methacrylate) and poly(oxypropyl) acrylate (or methacrylate). Fluorinated and/or ruthenium interfacial activity Reality of surfactant other than agent Examples include nonionic surfactants such as polyoxyethylene ethyl ether, polyoxyethylene ethyl propyl ether, polyoxyethylene ethyl/polyoxypropyl propylene block copolymer, sorbitan Aliphatic esters, and polyoxyethylene sorbitan esters. • These surfactants can be used singly or in combination. The surfactant is preferably used in the total amount of the positive photosensitive composition (except solvent). It is used in an amount of 0.000 to 2% by mass, more preferably 0.001 to 1% by mass. It may be added (G) having at least one selected from the group consisting of an alkali-soluble group, a hydrophilic group and an acid-decomposable group, and having a molecular weight of not more than 3,000. The dissolution inhibiting compound (hereinafter referred to as "dissolution inhibiting compound"). As the dissolution inhibiting compound (G), it is preferably a compound having an alkali-soluble group (for example, a fluoroalkyl-substituted carboxyl group, a sulfonyl sulfoximine group or a gastric group at -α-position of -74-200844664), a compound having a hydrophilic group (such as a hydroxyl group, a lactone group, a cyano 'guanidino group, a pyrrolidinyl group, or a sulfonylamino group), or having an action of a ® acid to decompose to release an alkali-soluble or hydrophilic group thereof a compound based on it. The group which releases the alkali-soluble group or the hydrophilic group by decomposition by an acid is preferably a carboxyl group or a hydroxyl group which is protected by an acid-decomposable group. In order to prevent the decrease in the transmittance at 220 nm or less, it is preferred to use an aromatic ring-free compound or an amount of the aromatic ring-containing compound in an amount of not more than 20% by weight based on the solid content of the composition as dissolution inhibition. Compound. Preferable examples of the dissolution inhibiting compound include a carboxylic acid compound having an alicyclic hydrocarbon structure (e.g., adamantane (di) carboxylic acid, norbornanecarboxylic acid and cholic acid), and a compound obtained by protecting the carboxylic acid with an acid decomposable group. , a polyol (such as a sugar), and a compound obtained by protecting a hydroxyl group of the polyol with an acid decomposable group. In the present invention, the dissolution inhibiting compound has a molecular weight of not more than 3,000, preferably from 300 to 3,000, more preferably from 500 to 260. The dissolution inhibiting compound is added in an amount of preferably from 3 to 40% by mass, more preferably from 5 to 20% by mass, based on the solid content of the positive photosensitive composition. The following are designated examples of the dissolution inhibiting compound, but the invention is not limited thereto. -75- 200844664

43⁄4 TB-10 -OH H0-iCH2)12-0H TB-11 OH H0 OH TE-12

HO* HOT

TE-13

OH

TE-14

^l^^C0NHS02Me TE-15 ΤΕΊβ &lt;Other Additives&gt; The positive photosensitive composition of the present invention may further contain additives such as a dye, a plasticizer, a sensitizer, and a compound which accelerates dissolution in a developer as needed. . The compound which can be used in the present invention to accelerate dissolution in a developer is a low molecular compound having a molecular weight of not more than 1,000 and having two or more phenolic oxime groups or one or more carboxyl groups. If it has a carboxyl group, the compound is preferably an alicyclic or aliphatic compound. The dissolution accelerating compound is added in an amount of preferably 2 to 50% by mass, more preferably 5 to 30% by mass, based on the acid-decomposable resin. From the viewpoint of reducing development residue and preventing pattern deformation during development, it is preferred that the amount is not more than 50% by mass. The phenolic compound having such a molecular weight of not more than 1,000 can be referred to by the skilled artisan, for example, JP. -A-4- 1 2293 8 and JPU-2853 No. 1 patent, U.S. Patent No. 4,9,16,210, and European Patent No. 2,199,294 are readily synthesized. Specific examples of the carboxyl group-containing alicyclic or aliphatic compound include, but are not limited to, carboxylic acid derivatives having a steroid structure (such as cholic acid, deoxycholic acid and lithocholic acid), adamantanecarboxylic acid derivatives, and adamantane dicarboxylic acid. , cyclohexanecarboxylic acid, and cyclohexane dicarboxylic acid. (Pattern forming method) Φ The positive photosensitive composition of the present invention is obtained by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, and filtering the resulting solution, and coating the filtrate in a predetermined support as described below. Use it physically. The filter for filtration is preferably made of polytetrafluoroethylene, polyethylene or nylon, and has a porosity of 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. For example, a positive photosensitive composition is coated on a substrate for manufacturing a precision integrated circuit device (for example, a tantalum/cerium oxide substrate) by a suitable coating method such as a spin coater or an applicator. It is then dried to form a photosensitive film. The photosensitive film is exposed to light-like radiation or radiation through a predetermined mask, preferably baked (heated), then developed and washed, whereby a good pattern can be obtained. During light-like or radiation exposure, the exposure is preferably carried out by immersing a liquid having a higher refractive index than air (impregnation medium) between the photosensitive film and the lens (immersion exposure). The immersion exposure can enhance the resolution. The impregnating medium can be any liquid 'as long as its refractive index is higher than air, but is preferably pure water. In order to prevent the impregnating medium from directly contacting the photosensitive film during the immersion exposure, it can provide a topcoat layer on the photosensitive film. This prevents the composition from being released from the photosensitive film into the impregnation medium to reduce development defects. Before the photosensitive film is formed, it may be coated on the substrate in advance to form an anti-reflection film. As the antireflection film, an inorganic film made of titanium, titanium oxide, titanium nitride, chromium oxide, carbon, or amorphous germanium, or one of an organic film made of a light absorbing agent and a polymer material can be used. As for the organic anti-reflection film, a commercially available organic anti-reflection film such as Brewer Science's "DUV-30 Series" _ or "DUV-40 Series" (trade name) or Shipley's "AR-2" may be used. "AR-3" or "AR-5" (trade name). Examples of light-like radiation or radiation include infrared rays, visible light, ultraviolet rays, far ultraviolet rays, X-rays, and electron beams. Among them, a wavelength of 25 nm or less, more preferably 220 nm or less, is preferred. Designated examples include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 excimer laser light (157 nm), X-ray, and electron beam, of which ArF is preferred. Molecular laser light, F2 excimer laser light, EUV • (13 nm), and electron beam. In the developing step, the alkali developer is used as follows. The photoresist composition uses an alkali developer as an alkaline aqueous solution, such as an inorganic base (such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, or aqueous ammonia), a primary amine (such as ethylamine or positive). Propylamine), a secondary amine (such as diethylamine or di-n-butylamine), a tertiary amine (such as triethylamine or methyldiethylamine), an alcoholamine (such as dimethylethanolamine or triethanolamine), a quaternary ammonium An aqueous solution of a salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide or a cyclic amine such as pyrrole or piperidine. -78- 200844664 It is also possible to use the above alkali developer to which an appropriate amount of alcohol or 'surfactant has been added. The alkali developer has an alkali concentration of generally 0.1 to 20% by mass. The alkali developer has a pH of generally from 10.0 to 15.0. [Example 1] The present invention is further described in detail below by way of examples. However, it is to be understood that the invention is not limited thereto. Synthesis Example: Synthesis of Resin (C) • 22.21 g of 1,1,1,3,3,3-hexafluoropropan-2-acrylate and 22.43 g of 4-tert-butyl methacrylate were dissolved in propylene glycol-A Ether acetate was used to prepare a solution of 20 5.36 g of a solids concentration of 20%. To the resulting solution, 3.0 mol% (1.382 g) of a polymerization initiator "V601" (trade name, product of Wako Pure Chemical Industries) was added. The resulting mixture was added dropwise to 17.86 g of propylene glycol monomethyl ether acetate heated to 80 ° C over 4 hours under nitrogen atmosphere. After the end of the dropwise addition, the reaction mixture was stirred at 80 ° C for 2 hours. The reaction mixture was cooled to room temperature, and then added dropwise to a volume of 5··1 methanol:water mixed solvent as the amount of the reaction mixture. The thus precipitated solid was collected by filtration to give 35.6 g of the desired product HR-19. This resin has a weight average molecular weight of 7 800 and a dispersibility of 2.0 as measured by GPC with respect to polystyrene standards. Other resins were prepared similarly. &lt;Photoresist Preparation&gt; The components shown in the following Table 2 were dissolved in a solvent to prepare a solution having a solid content of -79 to 200844664 and a mass ratio of 7 mass%. The resulting solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a positive resist solution. The positive resist composition thus prepared was evaluated by the following method, and the results are shown in the following table. When using multiple ingredients, the mass ratio is shown in the table. [Imaging performance test] (Exposure 1) An organic anti-reflective coating "ARC291" (trade name; product of Nissan Chemical) was coated on a sand wafer, and then baked at 205 ° C for 60 seconds to form 78 nm. Anti-reflective film. Then, the positive-type photoresist group φ prepared above was applied to an anti-reflection film, and then baked at 120 ° C for 60 seconds to prepare a 250 nm photoresist film. The thus obtained wafer acceptance pattern is exposed by an ArF excimer laser scanner ("PAS5500/1 1 00", trade name; ASML product, NA··0.75, σ0/σ1=0·85/0·55) . After heating at 120 °C for 60 seconds, it was continuously developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by weight) for 30 seconds, washed with pure water, and spin-dried to obtain a photoresist pattern. (Exposure 2) This condition is for forming a photoresist pattern using pure water in accordance with immersion exposure. • Organic anti-reflective coating "ARC291" (trade name; Nissan

The Chemical product was coated on a tantalum wafer and baked at 205 ° C for 60 seconds to form a 78 nm anti-reflective film. Then, the positive resist group prepared above was applied to an antireflection film, followed by baking at 120 ° C for 60 seconds to prepare a 250 nm photoresist film. The thus obtained wafer was subjected to pattern exposure by an A r F excimer laser scanner (N A : 0.7 5 ). As for the immersion liquid, ultrapure water having an impurity concentration of not more than 5 ppb is used. After heating at 1200 °C for 60 seconds, it was continuously developed with an aqueous solution of tetramethylammonium hydroxide (2·38 wt%) for 30 seconds, washed with pure -80-200844664 water, and spin-dried to obtain a photoresist pattern. [Evaluation of Line Edge Thickness] Line edge thickness (LER) was evaluated by observing a 120 nm separation pattern by a length measurement scanning electron microscope (SEM) using a length measurement SEM (,, S-8 840", Trademark name; product of Hitachi, Ltd.) The longitudinal edge of the 5 micron range relative to the line pattern is measured at 50 points, and the reference line should be measured at the edge, and the standard deviation is calculated and calculated as 3 σ. The unit is nanometer. Smaller performance is better. Φ [Water follow-up force] The positive resist composition solutions prepared above are coated on a germanium wafer and baked at 1 15 ° C for 60 seconds to form a 200 nm photoresist film. As shown in Fig. 1, 15 ml of distilled water is dropped on the central portion of the wafer 1 having the photoresist film formed thereon, and then 10 square centimeters of quartz plate 3 having the kite line 2 is placed in distilled water clay. The entire space between the wafer 1 and the quartz plate 3 is filled with distilled water 4. Next, the wafer 1 is fixed and the kite wire 2 attached to the quartz plate 3 is wound to rotate the motor 5 at a speed of 30 cm/sec. Member. Drive motor 5 for 0 · 5 seconds to move quartz plate 3. Move on quartz plate 3 After the movement, the amount of distilled water remaining under the quartz plate 3 was evaluated according to the following criteria and using the index of water follow-up force. Figures 2A to 2D slightly describe various patterns observed from above after the movement of the quartz plate 3. The oblique line portion 6 is a region of distilled water remaining under the quartz plate 3, and the blank portion 7 is a region where distilled water cannot follow the movement of the quartz plate 3 and the air has entered therein. -81 - 200844664 As described in Fig. 2A, even in the quartz plate 3 After the movement, the distilled water remains on the entire surface of the substrate, and the following force of the water is evaluated as A; as described in FIG. 2B, the following force of the water is obtained when the area where the air has entered does not exceed about 10% of the total substrate area. Graded as B; as depicted in Figure 2C, when the area of air that has entered is 20% or more but less than 50% of the total substrate area, the water follow force is evaluated as C; and as depicted in Figure 2D, The water following force is rated as D when the area in which the air has entered is about 50% or more of the total substrate area.

Composition Result Resin Oxygen Agent Solvent Hydrophobic Interface LER LER Water (2g) (mg) (Weight Ratio) Resin (C) Active Agent (Condition 1) (Condition 2) Following Force (mg) ( Mg) (mg) Comparative Example 1 RX Ρ-13 SL-1/SL-4 Ν-1 - W-1 19 18 D (10) 60/40 (7) (3) Comparative Example 2 RX Ρ-13 SL-1/SL- 4 Ν·1 HR-19 W-1 16 16 Β (80) 60/40 (7) (80) (3) Example 1 RA-1 Ρ-13 SL-1/SL-4 Ν-1 HR-19 W-1 14 14 Β (8〇) 60/40 (7) (80) (3) Example 2 RA-1 Ρ-11 SL-1/SL-4 Ν-1 HR-19 W-1 13 13 Β (80) 60/40 (7) (80) (3) Example 3 RA-1 Ρ-11 SL-1/SL-2 Ν-1 HR-19 W-1 12 12 Β (8〇) 60/40 (7) (80) (3) Example 4 RA-1 Ρ-11 SL-1/SL-3 Ν-1 HR-19 W-1 12 12 Β (10) 60/40 (7) (80) (3) Example 5 RA-1 Ρ-11 SL-1/SL-2 Ν -2 HR-19 W-1 11 11 A (8〇) 60/40 (7) (80) (3) Example ό RA-1 Ρ-11 SL-1/SL-2 Ν-3 HR-19 W-1 11 11 B (80) 60/40 (7) (80) (3) Example 7 RA-1 Ρ-1 SL-1/SL-4 Ν-1 HR-19 W-1 12 12 B _ 60/40 (7) (80) (3) Example 8 RA-1 Ρ-2 SL-1/SL-4 Ν-1 HR-19 W-1 12 12 B (8〇) 60/40 (7) (80) 0) Example 9 RA-1 Ρ-3 SL-1/SL-4 Ν-1 HR-19 W-1 10 9 B ( 80) 60/40 (7) (80) (3) -82- 200844664

Example 10 RA-1 P-4 (80) SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W-1 (3) 11 12 A Example 11 RA-1 P-5 (80 SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W-1 (3) 12 12 B Example 12 RA-1 P-6 (80) SL-1/SL-4 60/ 40 N-1 (7) HR-19 _ W-1 (3) 11 10 B Example 13 RA-1 P-7 (80) SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W -1 (3) 12 12 B Example 14 RA-1 P-8 (80) SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W-1 (3) 10 9 B Example 15 RA-1 P-9 (80) SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W-1 (3) 13 12 B Example 16 RA-1 P-10 (8 〇) SL-1/SL-4 60/40 N-1 (7) HR-19 (B0) W-1 (3) 13 12 B Example 17 RA-1 P-12 (8〇) SL-1/SL-4 60/40 N-1 (7) HR-19 (80) W-1 (3) 13 12 B Example 18 RA-2 P-1 _ SL-1/SL-2 60/40 N-5 (7) HR-19 (80) W-1 (3) 11 10 B Example 19 RA-3 P-2 (80) SL-1/SL-2 60/40 N-2 (7) HR-04 _ W-1 (3) 12 11 A Example 20 RA-4 P-3 (80) SL-1/SL-2 60/40 N-3 (7) HR-10 (80) W-1 (3) 11 11 B Example 21 RA-5 P-4 (8 〇) SL-2/SL-4/SL-6 40/59/1 N-2 (9) HR-15 (35) W-1 (3) 9 9 B Example 22 RA-6 P-5 (100) SL-2/SL-4 70/30 N-6 (7) HR-21 (60) W-4 (4) 10 10 A Example 23 RA-7 P-6 (40 /60) SL-2/SL-4 60/40 N-1 (7) HR-25/HR-10 (20/30) W-1 (3) 11 10 A Example 24 RA-8 P-7 (20 /80) SL-1/SL-2 50/50 N-2 (6) HR-22 (8〇) W-4 (3) 11 11 B Example 25 RA-9 P-8 (110) SL-1/ SL-2 30/70 N-5 (7) HR-25 (60) W-5 (5) 8 8 A Example 26 RA-10 P-9 (120) SL-3/SL-4/SL-6 40/59 /1 N-4 (7) HR-29 (90) W-1 (3) 7 7 B Example 27 RA-11 P-10/P-9 (40/60) SL-2/SL-3 60/40 N-2 (6) HR-30 (80) W-2 (3) 9 9 B Example 28 RA-12 P-12/P-9 (100/10) 'SL-2/SL-3 60/40 - HR-31 (10) W-4 (5) 10 9 A

The symbols used in Table 2 each have the following meanings. The structure and the like of the acid-decomposable resin (A) used in the examples are shown below. -83- 200844664

Kw=6200 Mvsr/Mn=l. 63

Mw=830❹ ^/Mn=l. 70

Mw=13800 Mw/Mn^l. 80

Mw=5800 Mw/Mn=l. 52

Mw=6600 Mw/Mn=l, 55

-84- 200844664

Mw=6800

Mw=10800 Ww/Mn-1.79

(RA-11) (RAr12)

BAWS19200 Mw/Mn-190

Mw=8400 Mw/Mn; 1.59

Mvf6100 Kw/lln=l. 61 The structure of the compound (B) used in the examples is shown below. -85 - 200844664

N〇2 ^§:〇3S

O3S

(P-3)

(P-4) (P-5)

(P-6)

(P-7) _Q•〇2s^Y°^Q

(P-9) CF3(CF2)sSCV (P-11)

(P-8) , s〇 (P-10) cf3 (cf fine r 5 ^_o-^so3h (P-12) (p-13)

Nl : N,N-dibutylaniline N-2 : N,N-dihexylaniline N-3 : 2,6-diisopropylaniline N-4: Tri-n-octylamine N-5 : Ν, Ν- Dihydroxyethylaniline Ν-6 : Ν,Ν-dihexylaniline

Chemicals W-1 : "Megaface F176" (trade name; product of Dainippon Ink) (fluorine-containing) -86- 200844664 W-2: "Megaface R08" (trade name; product of Dainippon Ink & Chemicals) (fluorine-containing and矽) W-3: Polyoxane polymer "KP-341" (trade name; product of Shin-Etsu Chemical) (including sand) W-4·· "Troysol S-36 6" (trade name; Troy Corporation Product) W-5 : "PF6 5 6" (trade name; OMNOVA product, fluorine) W - 6 : "PF 6 3 2 0 " (trade name; 〇MN Ο VA product, fluorine) SL - 1 ··cyclohexanone φ SL-2: propylene glycol monomethyl ether acetate SL-3: 2-heptanone SL - 4 : propylene glycol monomethyl ether SL - 5 : γ - butyrolactone SL-6: carbonic acid The ester is apparent from the results of Table 2, and the photosensitive composition of the present invention has excellent water follow-up force during immersion exposure and has low line edge roughness. SUMMARY OF THE INVENTION The present invention provides a positive-type photoresist composition which has a small edge edge thickness due to normal exposure or immersion exposure and excellent water follow-up force during immersion exposure; and a pattern forming method using the composition. The entire disclosure of each of the foreign patent applications for which the priority of the priority is claimed in the present application is hereby incorporated by reference in its entirety. [Simple description of the drawing] Fig. 1 is a schematic view (side surface) of the evaluation of the water following force. Figures 2 to 2D are schematic views of the evaluation of water follow-up force (top view). -87- 200844664 [Description of main component symbols] 1 Wafer 2 Kite line 3 Quartz plate 4 Steaming water 5 Motor 6 Slash part 7 Blank part

-88

Claims (1)

200844664 X. Patent application scope: 1. A positive-type photoresist composition comprising: (A) an acid-decomposable repeating unit represented by formula (I) and increasing its alkali-developing agent by the action of an acid a medium-soluble resin; (B) a compound which generates an acid upon irradiation with light-like radiation or radiation; (C) a hydrophobic resin which is insoluble in an alkali developer and has at least one of a fluorine atom and a halogen atom; (D) a solvent, Wherein in the formula (I), a hydrogen atom, an alkyl group, a cyano group or a halogen atom is represented. Ryi to Ry3 each independently represent an alkyl group or a cycloalkyl group, and Ryi to at least two may be bonded to form a ring structure, and z represents a divalent bond group. 2. The positive-type photoresist composition according to claim 1, wherein Z in the formula (I) is a divalent linear hydrocarbon group or a divalent cyclic hydrocarbon group. 3. The positive-type photoresist composition according to claim 1, wherein the resin (A) further has a repeating unit having at least one selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and an acid group. 4. The positive-type photoresist composition of claim 1, wherein the compound (B) comprises an acid-generating compound represented by the formula (BII): -89- 200844664 (Rb^m (丨)&quot;S〇3H (Rb^n (BII)) In the formula (BII), Rh represents a group having an electron attracting group, and Rb2 represents an organic group having no electron attracting group, m and η Each represents an integer of 〇 to 5, with the condition that m + I] when m is 2 or more, a plurality of Rb! may be the same or when η is 2 or more, 'multiple Rt> 2 may be the same or The positive-type photoresist composition of claim 4, wherein in the formula (BII), m is 1 to 5 and at least one of the electrons of the RIm is selected from a fluorine atom, a fluoroalkyl group, a nitro group, and an ester. A positive-type photoresist composition according to claim 1, wherein the resin (C) has at least one fluorine-containing repeating unit selected from the formula (1, 1} (1-3) The repeating unit is soluble in the alkali developer: &lt;5 &gt; the same, and the same. The attracting group is the cyano group, (1-2) and stable and not (1-1) (1-2) (1-3) wherein, in the formulae (1-1) to (1-3), Ri represents a hydrogen atom or an alkyl group, and R2 represents a fluorine-based group, -90- 200844664 R3 Represents a hydrogen atom or a monovalent organic group, and R4 to R7 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkoxy group. The condition is that at least one of R4 to R7 represents a fluorine atom, or r4 and R5 or R6 and r7 May form a ring, h represents a hydrogen atom, a fluorine atom or a monovalent organic group, Rf represents a fluorine atom or a monovalent organic group having a fluorine atom, L represents a single bond or a divalent bond group, Q represents an alicyclic structure, and _ k is an integer from 〇 to 3. 7. The positive-type photoresist composition according to claim 1, wherein the resin (C) has at least one of a fluorene-containing repeating unit represented by the formula (CI) and a fluorene-containing repeating unit represented by the formula (CII), Stable in acid and insoluble in alkaline developer: Wherein in the formulae (CI) and (CII), Lc represents a single bond or a divalent bond, and Re i each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkoxy group. A carbonyl group, Rc2 represents a monovalent organic group having at least one deuterium atom, Rq represents a hydrogen atom, a halogen atom, a cyano group, or a monovalent organic group, and -91 - I I 200844664 Qc represents an alicyclic structure, and kc is an integer of 0 to 3. 8. The positive-type photoresist composition according to claim 1, wherein the resin (C) is at least one of the following: (C1) a resin having at least one of a fluorine atom and a halogen atom; and an alicyclic structure; And (C2) - a repeating unit having at least one of a fluorine atom and a halogen atom in a side chain thereof; and a repeating unit having an unsubstituted alkyl group in a side chain thereof. 9. A positive-type photoresist composition as claimed in claim 1 for exposure to light having a wavelength of 200 nm or less. iO. A pattern forming method comprising: forming a photoresist film from a positive photoresist composition of claim 1; and exposing and developing the photoresist film. U. The pattern forming method of claim 1, wherein the photoresist film is exposed to the immersion liquid. -92 -