JP2010139996A - Resist composition for negative development and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition for negative development excellent in line width variation (LWR), exposure latitude (EL) and focal depth allowance (DOF) in order to stably form a high accuracy fine pattern for the manufacture of a highly integrated and high accuracy electronic device, and a pattern forming method using the same. <P>SOLUTION: The resist composition for negative development includes (A) a resin which has an acid decomposable repeating unit and exhibits increased polarity and decreased solubility in a negative developer under the action of an acid, (B) a photoacid generator which generates an acid having one or two fluorine atoms upon irradiation with actinic rays or radiation, and (C) a solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a negative developing resist composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes, and a pattern using the same. The present invention relates to a forming method. In particular, the present invention relates to a negative developing resist composition suitable for exposure with an ArF exposure apparatus and an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same. is there.

  Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. When exposed, the acid generator in the exposed area decomposes to generate an acid, and the acid generated in the exposure bake (PEB) is a reaction catalyst. Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

With the miniaturization of semiconductor elements, the wavelength of an exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed. These can be expressed by the following equations as is generally well known.
(Resolving power) = k ₁ · (λ / NA)
(Depth of focus) = ± k ₂ · λ / NA ²
Where λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

As a technique for increasing the resolving power, a so-called immersion method in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between the projection lens and the sample has been proposed.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The above-described resolving power and depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

Further, as a technique for further improving the resolution, a double exposure technique (Double Exposure Technology) and a double patterning technique (Double Patterning Technology) have been proposed. This is to reduce k ₁ in the above-described resolving power formula, and is positioned as a technique for increasing the resolving power.

Conventionally, pattern formation of electronic devices such as semiconductor elements is performed by reducing and transferring a mask or reticle pattern, which is 4-5 times the size of the pattern to be formed, to an object to be exposed such as a wafer using a reduction projection exposure apparatus. It was.
However, with the miniaturization of dimensions, the conventional exposure method has a problem in that the light irradiated to adjacent patterns interferes with each other and the optical contrast is reduced. The design is divided into two or more, each mask is exposed independently, and an image is synthesized. In these double exposure methods, it is necessary to divide the design of the exposure mask, re-synthesize the image on the object to be exposed (wafer), and the pattern on the reticle faithfully adheres to the object to be exposed. It is necessary to devise the division of the mask design so that it can be reproduced.
An example in which the effect of these double exposure methods is studied for transferring a fine image pattern of a semiconductor element is introduced in Patent Document 1 and the like.

  However, if the conventional resist composition is simply applied to the conventional resist process for pattern formation, these double exposure methods require pattern formation near the resolution limit of the resist. The problem is that a large exposure margin and depth of focus cannot be obtained.

Currently, various developers for g-line, i-line, KrF, ArF, EB, and EUV lithography have been proposed. An aqueous alkaline developer of 2.38% by mass TMAH (tetramethylammonium hydroxide) is used. It is used for general purposes.
However, it is of course desirable to form a pattern with a comprehensively good performance, but it is extremely difficult to find an appropriate combination of resist composition, developer, rinse solution, and the like necessary for that purpose. This was the actual situation, and improvements were required. In particular, as the resolution line width of the resist becomes finer, improvements in line edge roughness performance of line patterns and in-plane uniformity of pattern dimensions have been demanded.

Moreover, in the combination of a conventional resist composition and a developer, a system for forming a pattern by combining a specific resist composition with a developer containing a high polarity alkaline developer or a low polarity organic solvent is provided. Only. That is, as shown in FIG. 1, in a positive system (combination of a resist composition and a positive developer), a region having a high light irradiation intensity in a spatial frequency of an optical image is selectively dissolved and removed. Only materials for patterning are provided. On the other hand, the negative system (resist composition and negative developer) only provides a material system that selectively dissolves and removes areas with low light irradiation intensity to form a pattern. .
Here, the positive developer is a developer that selectively dissolves and removes the exposed portion that is equal to or higher than the predetermined threshold shown by the solid line in FIG. 1. The negative developer is lower than the predetermined threshold. A developer that selectively dissolves and removes the exposed portion. The development process using a positive developer is referred to as positive development (also referred to as a positive development process), and the development process using a negative developer is referred to as a negative development (also referred to as a negative development process). Call.

On the other hand, Patent Document 2 discloses a double development technique as a double patterning technique for increasing resolution. In this example, a general chemical amplification image forming method is used, and by exposure, the polarity of the resin in the resist composition becomes high in a region where the light intensity is high, and low in a region where the light intensity is low. By utilizing this, positive development is performed by dissolving a high exposure area of a specific resist film in a high polarity developer, and negative development is performed by dissolving a low exposure area in a low polarity developer. . Specifically, as shown in FIG. 2, a region where the exposure amount E2 of the irradiation light 1 is dissolved using an alkaline aqueous solution as a positive developer, and a region where the exposure amount E1 is less than a specific organic solvent is negatively developed. It is dissolved as a liquid. As a result, as shown in FIG. 2, an intermediate exposure amount (E2-E1) region remains without being developed, and an L / S pattern 3 having a half pitch of the exposure mask 2 is formed on the wafer 4. Yes.
However, it is very difficult to select an optimal combination of a resist composition and a negative developer, and in the above example, developability when using a negative developer is deteriorated. There was a problem.
Furthermore, when forming a fine pattern by double development, it is not sufficient that the resolving power when using a negative developer or a positive developer alone is sufficient, and the negative developer and the positive developer are not sufficient. In either case, it has been required to exhibit good pattern resolution.

In view of the above problems, pattern formation using a positive resist composition in which the solubility in a positive developer is increased and the solubility in a negative developer is decreased by irradiation with actinic rays or radiation in the double development technique. A method is proposed in US Pat. According to this technique, it is said that a highly accurate fine pattern can be stably obtained.
However, it is required that a fine pattern with higher accuracy can be stably obtained by excellent line width variation (LWR), exposure latitude (EL), and focus margin (DOF).

JP 2006-156422 A JP 2000-199953 A US Patent Application Publication No. 2008/0187860

  The present invention solves the above-described problems, and in order to more stably form a high-precision fine pattern for manufacturing a highly integrated and high-precision electronic device, line width variation (LWR), exposure latitude (EL) It is another object of the present invention to provide a negative developing resist composition excellent in focus margin (DOF) and a pattern forming method using the same.

  The present invention has the following configuration, whereby the above object of the present invention is achieved.

  (1) (A) a resin containing a repeating unit having a group having a lactone structure represented by the following general formula (1), which increases its polarity by the action of an acid and decreases its solubility in a negative developer. A negative resist composition for development.

In general formula (1),
R ₂ independently represents a chain or cyclic alkylene group. When there are a plurality of R _{2 s} , they may be the same or different.
R ₃ each independently represents an alkyl group or a cycloalkyl group. When there are a plurality of R _{3 s,} they may be the same or different, and two R ₃ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently. When there are a plurality of Y, they may be the same or different.
Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, they may be the same or different.
k is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

  (2) The repeating unit having a group having a lactone structure represented by the general formula (1) is a repeating unit having a lactone structure represented by the following general formula (2) (1) A negative resist composition for development according to 1.

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group or a halogen atom.
_{R 2, R 3, X,} Y, Z, k, n, m are each, in general formula (1) _{in, R 2, R 3, X} , Y, Z, k, n, in m synonymous is there.

  (3) (a) A step of forming a film with the negative developing resist composition described in (1) or (2), (a) an exposure step, and (d) development using a negative developer. A pattern forming method comprising the steps of:

  (4) The negative developer is a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. The pattern formation method as described in (3).

  (5) The resin is a resin whose polarity is increased by the action of an acid to increase the solubility in a positive developer, and (c) further includes a step of developing using a positive developer. (3) or the pattern formation method as described in (4).

  According to the present invention, it is possible to provide a negative developing resist composition excellent in line width variation (LWR), exposure latitude (EL), and focus margin (DOF), and a pattern forming method using the same.

Hereinafter, the best mode for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  First, terms used in this specification will be described. There are two types of pattern formation methods: positive and negative. Both use the fact that the solubility of the resist film in the developer changes due to a chemical reaction triggered by light irradiation. The case where the part is dissolved in the developer is called a positive type, and the case where the non-irradiated part is dissolved in the developer is called a negative type. There are two types of developers used in this case, a positive developer and a negative developer. The positive developer is a developer that selectively dissolves and removes the exposed portion above the predetermined threshold indicated by the solid line in FIG. 1, and the negative developer selects the exposed portion below the predetermined threshold. It is a developer that is dissolved and removed. The development process using a positive developer is referred to as positive development (also referred to as a positive development process), and the development process using a negative developer is referred to as a negative development (also referred to as a negative development process). Call. Multiple development (also referred to as multiple development process) is a development system that combines a development process using the positive developer and a development process using the negative developer. In the present invention, the resist composition used for negative development is called a negative development resist composition, and the resist composition used for multiple development is called a multiple development resist composition. Hereinafter, when it is simply described as a resist composition, it means a negative developing resist composition. The negative type rinsing liquid represents a rinsing liquid containing an organic solvent, which is used in the washing step after the negative type developing step.

  In the present invention, as a technique for increasing the resolving power, as shown in FIG. 3, a developer (negative developer) that selectively dissolves and removes an exposed portion having a predetermined threshold value (b) or less, and a polarity by the action of an acid. Increases the solubility in a positive developer (preferably an alkali developer) and decreases the solubility in a negative developer (preferably an organic developer) by irradiation with actinic rays or radiation. A new pattern forming method is proposed in combination with a negative developing resist composition for forming a film.

The negative development resist composition of the present invention exhibits excellent development characteristics even with respect to a developer (positive developer) that selectively dissolves and removes an exposed area having a predetermined threshold value (a) or more. Developer (positive developer) that selectively dissolves / removes exposed portions that are equal to or higher than the threshold value (a) and developer solution that selectively dissolves / removes exposed portions that are equal to or lower than a predetermined threshold (b) (negative development). (Liquid) and a resist composition for negative development can be combined to form a pattern by multiple development.
That is, as shown in FIG. 3, when a pattern element on an exposure mask is projected onto a wafer by light irradiation, a region having a high light irradiation intensity (an exposed portion having a predetermined threshold value (a) or more) is positively positioned. An optical aerial image (light) is obtained by dissolving / removing with a mold developer and dissolving / removing an area with a low light irradiation intensity (exposed portion below a predetermined threshold (b)) with a negative developer. A pattern having a resolution twice the frequency of the intensity distribution can be obtained.

  Therefore, the negative developing resist composition of the present invention can be suitably used as a multiple developing resist composition.

A pattern forming process necessary for carrying out the present invention includes the following steps.
(A) (A) It contains a repeating unit having a group having a lactone structure represented by the general formula (1) (described in detail later), and the polarity is increased by the action of an acid and the solubility in a negative developer is decreased. Forming a film with a negative developing resist composition characterized by containing a resin;
(A) an exposure process;
(D) a pattern forming method comprising a step of developing using a negative developer.

  In the pattern forming method of the present invention, the negative developer is a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. It is preferable.

  The pattern forming method of the present invention preferably further includes a step of developing the resin with a positive developer by increasing the polarity by the action of an acid and increasing the solubility in a positive developer. .

  The pattern forming method of the present invention preferably further includes (f) a step of washing using a rinse solution containing an organic solvent.

  The pattern forming method of the present invention preferably includes (e) a heating step after (b) the exposure step.

  The pattern formation method of this invention can have (b) exposure process in multiple times.

  The pattern formation method of this invention can have (e) a heating process in multiple times.

In carrying out the present invention, (A) a negative developer containing a repeating unit having a group having a lactone structure represented by the general formula (1) (to be described in detail later) and increasing the polarity by the action of an acid And a negative developing resist composition characterized by containing a resin whose solubility is reduced, and (Ab) a negative developing solution (preferably an organic developing solution).
In order to carry out the present invention, it is further preferred to use (Ac) positive developer (preferably an alkali developer).
In order to carry out the present invention, it is preferable to use a negative developing rinse solution containing (Ad) an organic solvent.

  In the case of performing a pattern formation process using two types of developers, a positive developer and a negative developer, the order of development is not particularly limited, but after the first exposure, the positive developer or negative developer is used. It is preferable to perform development using a mold developer and then to perform negative or positive development with a developer different from the first development. Furthermore, after performing negative development, it is preferable to wash with a negative developing rinse containing an organic solvent.

As a method of forming a pattern, there are (a) a method using a chemical reaction such as polarity conversion, and (b) a method using a bond formation between molecules such as a crosslinking reaction and a polymerization reaction.
In resist material systems where the molecular weight of the resin increases due to intermolecular bonds such as cross-linking reactions and polymerization reactions, one resist material is positive for one developer and one for another developer. It was difficult to construct a system that would act on the negative type.

According to the present invention, one resist composition can simultaneously act as a positive type for a positive developer and as a negative type for a negative developer.
In the present invention, an alkaline developer (aqueous) can be used as the positive developer, and an organic developer containing an organic solvent can be used as the negative developer.
In addition, the resist composition contains a resin whose polarity is increased by the action of an acid, and a film whose solubility in a negative developer is decreased and the solubility in a positive developer is increased by irradiation with actinic rays or radiation. It is a “resin composition that forms”.
According to the resist composition of the present invention, it contains a resin whose polarity is increased by the action of an acid, and not only the solubility in a negative developer is reduced by irradiation with actinic rays or radiation, It is possible to simultaneously increase the solubility in the developer and reduce the solubility in the developer containing the organic solvent.

In the present invention, it is important to control the “threshold” of the exposure amount (the exposure amount at which the film is solubilized or insolubilized in the developer in the light irradiation region). That is, when performing pattern formation, the minimum exposure amount solubilized in a positive developer and the minimum exposure amount insolubilized in a negative developer so that a desired line width can be obtained are “threshold values”. It is.
The “threshold value” can be obtained as follows.
That is, when performing pattern formation, the minimum exposure amount solubilized in the positive developer and the minimum exposure amount insoluble in the negative developer are threshold values so that a desired line width can be obtained. .
More precisely, the threshold value is defined as follows.
When the residual film ratio with respect to the exposure amount of the resist film is measured, as shown in FIG. 4, the exposure amount at which the residual film ratio becomes 0% with respect to the positive developer, the threshold value (a), and the negative developer. On the other hand, an exposure amount at which the remaining film rate becomes 100% is defined as a threshold value (b).
For example, as shown in FIG. 5, by setting the exposure threshold (a) solubilized in a positive developer higher than the exposure threshold (b) solubilized in a negative developer, 1 A pattern can be formed by one exposure. That is, as shown in FIG. 6, first, a resist is applied to a wafer, and exposure is performed. First, a positive developing solution dissolves the exposure amount threshold (a) or more, and then a negative developing solution is used to expose the exposure amount threshold. (B) A pattern can be formed by one exposure by dissolving the following. In this case, the order of development with a positive developer and development with a negative developer may be first. After negative development, if a rinse solution containing an organic solvent is used for cleaning, a better pattern can be formed.

As a method for controlling the threshold value, there are a method for controlling a material-related parameter of the resist composition and the developer and a parameter related to the process.
As the material-related parameters, it is effective to control various physical property values related to the solubility of the resist composition in the developer and the organic solvent, that is, SP value (solubility parameter), LogP value, and the like. Specifically, the polymer weight average molecular weight, molecular weight dispersity, monomer composition ratio, monomer polarity, monomer sequence, polymer blend, addition of low molecular additives, and the developer contained in the resist composition, There are developer concentration, addition of low molecular additives, addition of surfactants, and the like.
Process-related parameters include film formation temperature, film formation time, post-exposure post-heating temperature, time, development temperature, development time, developing device nozzle method (liquid filling method), post-development rinsing method Etc.
Therefore, in the pattern formation method using negative development and the pattern formation method by multiple development using both negative development and positive development, in order to obtain a good pattern, the above-mentioned material-related parameters and process parameters are appropriate. It is important to control and combine them.

  The pattern formation process using two types of developer, a positive developer and a negative developer, may be performed by a single exposure as described above, or may be performed by a process of performing two or more exposures. Good. That is, after the first exposure, development is performed using a positive developer or a negative developer, and then, after the second exposure, with a developer different from the first development, Perform negative or positive development.

As an advantage of performing exposure twice or more, there is an advantage that the degree of freedom in controlling the threshold value in the development after the first exposure and the control of the threshold value in the development after the second exposure is increased. When performing the exposure twice or more, it is desirable to make the second exposure amount larger than the first exposure amount. As shown in FIG. 7, in the second development, the threshold is determined based on the sum of the first and second exposure history, but the second exposure is the first exposure. This is because if the amount is sufficiently larger than the amount, the influence of the first exposure amount becomes small and can be ignored in some cases.
Exposure at the first step of performing exposure ^{(Eo1 [mJ / cm 2]} ) , the exposure amount in the step of performing the second exposure ^{(Eo2 [mJ / cm 2]} ) than, 5 [mJ / cm ^2] or more Smaller is desirable. This can reduce the influence of the history of the first exposure on the pattern forming process by the second exposure.

  In order to change the exposure amount for the first time and the exposure amount for the second time, the above-described method of adjusting various parameters of the material / process is effective. In particular, the temperature of the first heating step and 2 It is effective to control the temperature of the second heating step. That is, in order to make the first exposure amount smaller than the second exposure amount, it is effective to set the temperature of the first heating step higher than the temperature of the second heating step.

The threshold value (a) in the positive development corresponds to the following in the actual lithography process.
After forming a film with a resist composition on a substrate that is irradiated with actinic rays or radiation, the solubility in a positive developer increases and the solubility in a negative developer decreases. Exposure is performed through a photomask having a pattern size. At this time, the exposure is performed while swinging the focus of exposure (focus) in increments of 0.05 [μm] and the exposure amount in increments of 0.5 [mJ / cm ² ]. After the exposure, heating is performed at a desired temperature for a desired time, and development is performed for a desired time with an alkali developer having a desired concentration. After the development, the line width of the pattern is measured using CD-SEM, exposure to form the desired line width A [mJ / cm ^2], determines the focus position. Next, the intensity distribution of the optical image when the previous photomask is irradiated at a specific exposure amount A [mJ / cm ² ] and a specific focus position is calculated. The calculation can be performed using simulation software (Prolith ver.9.2.0.15 manufactured by KLA). Details of the calculation method are described in Inside PROLITH (Chris. A. Mack, FINLE Technologies, Inc., Cahpter2 Aerial Image Formation).
As an example of the calculation result, a spatial intensity distribution of an optical image as shown in FIG. 8 is obtained.

  Here, as shown in FIG. 9, the light intensity at the position where the spatial position is shifted from the minimum value of the spatial intensity distribution of the optical image by 1/2 of the obtained pattern line width becomes the threshold value (a). Correspond.

The threshold value (b) in the negative development corresponds to the following in the actual lithography process.
A film made of a resist composition containing a resin whose polarity is increased by the action of an acid on a substrate, and increasing the solubility in a positive developer and reducing the solubility in a negative developer by irradiation with actinic rays or radiation. Then, exposure is performed through a photomask having a desired pattern size under desired illumination conditions. At this time, the exposure is performed while swinging the focus of exposure (focus) in increments of 0.05 [μm] and the exposure amount in increments of 0.5 [mJ / cm ² ]. After the exposure, heating is performed at a desired temperature for a desired time, and development is performed for a desired time with an organic developer having a desired concentration. After development, the line width of the pattern is measured using a CD-SEM, and an exposure amount A [mJ / cm ² ] and a focus position for forming a desired line width are determined. Next, the intensity distribution of the optical image when the previous photomask is irradiated at a specific exposure amount A [mJ / cm ² ] and a specific focus position is calculated. The calculation is performed using simulation software (Prolith manufactured by KLA).
For example, a spatial intensity distribution of an optical image as shown in FIG. 10 is obtained.

  Here, as shown in FIG. 11, the light intensity at a position where the spatial position is shifted by a half of the obtained pattern line width from the maximum value of the spatial intensity distribution of the optical image is set as the threshold (b). .

The threshold (a) is preferably 0.1 to 100 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], and still more preferably 1 to 30 [mJ / cm ² ]. The threshold (b) is preferably 0.1 to 100 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], and still more preferably 1 to 30 [mJ / cm ² ]. The difference between the threshold values (a) and (b) is preferably 0.1 to 80 [mJ / cm ² ], more preferably 0.5 to 50 [mJ / cm ² ], still more preferably 1 to 30 [mJ / cm ² ].

In the present invention, the film formed on the substrate includes (A) a repeating unit having a group having a lactone structure represented by the general formula (1) (described in detail later), and has a polarity by the action of an acid. It is a film formed by applying a negative developing resist composition characterized by containing a resin that increases and decreases its solubility in a negative developer.
Hereinafter, the resist composition that can be used in the present invention will be described.

(A) Resin having a repeating unit having a group having a lactone structure represented by the general formula (1), and having increased polarity by the action of an acid to reduce its solubility in a negative developer. The resin that increases in polarity by the action of an acid and decreases in solubility in a negative developer has a repeating unit having a group having a lactone structure represented by the following general formula (1).

In general formula (1),
R ₂ independently represents a chain or cyclic alkylene group. When there are a plurality of R _{2 s} , they may be the same or different.
R ₃ each independently represents an alkyl group or a cycloalkyl group. When there are a plurality of R _{3 s,} they may be the same or different, and two R ₃ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently. When there are a plurality of Y, they may be the same or different.
Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, they may be the same or different.
k is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

The group represented by R ₂ is not particularly limited as long as it is a chain alkylene group or a cyclic alkylene group, but a preferable chain alkylene group is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably. Has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. Preferable cyclic alkylene is C1-C20 cyclic alkylene, for example, cyclohexylene, cyclopentylene, norbornylene, adamantylene, etc. are mentioned. The group represented by R ₂ is preferably a chain alkylene. The chain alkylene group and the cyclic alkylene group are not particularly limited and may have a substituent. Examples of the substituent on the chain alkylene group and cyclic alkylene group include, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, Alkoxy groups such as benzyloxy group, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, t-butyl groups, pentyl groups, hexyl groups, etc., cyclopropyl, cyclobutyl, cyclopentyl, Examples thereof include cycloalkyl groups such as cyclohexyl group and cycloheptyl group, and cyano group, nitro group, sulfonyl group, silyl group, ester group, acyl group, vinyl group, aryl group and the like. When n is 2 or more, the groups represented by R ₂ may be independently the same or different.

The alkyl group represented by R ₃ preferably has 1 to 30 carbon atoms, more preferably a linear alkyl group or branched alkyl group having 1 to 15 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.
The cycloalkyl group as R ₃ is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The alkyl group and cycloalkyl group of R ₃ may have a substituent. Examples of the substituent on the alkyl group and cycloalkyl group include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, and benzyl. Alkoxy groups such as oxy groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, t-butyl groups, pentyl groups, hexyl groups and other alkyl groups, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl Group, cycloalkyl group such as cycloheptyl group, and cyano group, nitro group, sulfonyl group, silyl group, ester group, acyl group, vinyl group, aryl group and the like. In the case where there are a plurality of groups, two R ₃ groups may be bonded to form a ring (preferably a cycloalkylene group).

  X represents an alkylene group, an oxygen atom or a sulfur atom. As an alkylene group, a C1-C2 alkylene group is preferable and a methylene group, ethylene group, etc. are mentioned. Further, the alkylene group may have a substituent. Examples of such a substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, Alkoxy groups such as propoxy group, t-butoxy group and benzyloxy group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group and hexyl group Cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and cycloheptyl group, and cyano group, nitro group, sulfonyl group, silyl group, ester group, acyl group, vinyl group, aryl group and the like.

  Examples of the electron withdrawing group for Y include a cyano group, a nitro group, a carboxyl group, a hydroxy group or an alkoxy group, an alkoxycarbonyl group, and a halogenated alkyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, a benzyloxy group, and cyclohexaneoxy. The alkoxy group and the alkoxycarbonyl group may have a substituent. Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxy group, a methoxy group, and an ethoxy group. , Alkoxy groups such as isopropoxy group, t-butoxy group, benzyloxy group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, etc. Examples include cycloalkyl groups such as alkyl groups, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups, and cycloheptyl groups, and cyano groups, nitro groups, sulfonyl groups, silyl groups, ester groups, acyl groups, vinyl groups, and aryl groups. . Preferred Y is a cyano group, nitro group, hydroxy group, halogenated alkyl group, and particularly preferred Y is a cyano group.

  The group represented by Z includes a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, more preferably a single bond, an ether bond or an ester bond, particularly preferably. An ester bond. Z may be located on either the end side or the exo side of the norbornane skeleton.

  k is the number of substituents and represents an integer of 0 to 7, more preferably 0 to 5, particularly preferably 0 to 3. n represents the number of repetitions, and represents an integer of 1 to 5, more preferably 1 to 2. m is the number of substituents and represents an integer of 1 to 7. More preferably, it is 1-5, Most preferably, it is 1-3.

  The repeating unit having a group having a lactone structure represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group or a halogen atom.
R ₂ independently represents a chain or cyclic alkylene group. When there are a plurality of R _{2 s} , they may be the same or different.
R ₃ each independently represents an alkyl group or a cycloalkyl group. When there are a plurality of R _{3 s,} they may be the same or different, and two R ₃ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently. When there are a plurality of Y, they may be the same or different.
Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, they may be the same or different.
k is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

In the general formula _{(2), R 2, R} 3, X, Y, Z, k, n, m are in the general formula _{(1), R 2, R} 3, X, Y, Z, k , N and m.
The alkyl group for R ₁ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. The alkyl group may have a substituent. Preferred substituents on the alkyl group include a halogen atom, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an alkoxy group such as a benzyloxy group, and the like. Particularly preferred groups as R ₁ are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group.

  The repeating unit having a group having a lactone structure represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (3).

In general formula (3),
R _1a represents a hydrogen atom or an alkyl group.
When R _1a is an alkyl group (preferably having 1 to 10 carbon atoms), it may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a hydroxy group. It is done.
R ₃ each independently represents an alkyl group or a cycloalkyl group. When there are a plurality of R _{3 s,} they may be the same or different, and two R ₃ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
k is the number of substituents and represents an integer of 0 to 7.
l represents the number of repetitions and represents an integer of 1 to 5.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7.

In formula _{(3), R 3, X} , k, n, m are in the general formula _{(1), R 3, X} , k, n, is synonymous with m.
When R _1a is a halogenated methyl group, it is preferably a trifluoromethyl group.
Particularly preferred groups as R _1a are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group.
l is the number of repeating methylene groups and represents an integer of 1 to 5, more preferably an integer of 1 to 3.

The content of the repeating unit having a group having a lactone structure represented by the general formula (1) is preferably from 15 to 70 mol%, more preferably from 20 to 50 mol%, still more preferably based on all repeating units in the resin. 30 to 50 mol%.
It is particularly preferable from the viewpoint of developability that the repeating unit having a group having a lactone structure is ± 20 mol% of the molar ratio (mol%) of the acid-decomposable repeating unit described later.

  Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (1) are shown below, but the present invention is not limited thereto.

In the following specific examples, R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, and preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group or a halogen atom.

  As the repeating unit having a group having a lactone structure represented by the general formula (1), a (meth) acrylic acid ester derivative having a structure of the general formula (1), a (meth) acrylamide derivative, a vinyl ether derivative, an olefin derivative, Examples thereof include a repeating unit having a styrene derivative, and a repeating unit having a (meth) acrylic acid ester derivative having a structure of the general formula (I) is preferable.

  In addition to the repeating unit having the group having the lactone structure represented by the general formula (1), the resin of the component (A) has a lactone structure different from the group having the lactone structure represented by the general formula (1). It may have a repeating unit having a group. Any lactone structure can be used as long as it has a lactone structure, but a 5- to 7-membered lactone structure is preferable, and a bicyclo structure or a spiro structure is formed in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plural substituents (Rb ₂ ) may be the same or different, and the plural substituents (Rb ₂ ) may be bonded to form a ring. .

  Examples of the repeating unit having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-16) include a repeating unit represented by the following general formula (AI).

In general formula (AI),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ 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 obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by. Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-16).

  The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  The content of the repeating unit having a group having another lactone structure is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the resin.

Specific examples of the repeating unit having a group having another lactone structure are listed below, but the present invention is not limited thereto. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Examples of the resin used in the resist composition of the present invention that increases in polarity by the action of an acid and decreases its solubility in a negative developer include a repeating unit having a group having a lactone structure represented by the general formula (1) In addition, for example, the main chain or side chain of the resin, or both the main chain and the side chain have a group that decomposes by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”). Resin (hereinafter also referred to as “acid-decomposable resin” or “resin (A)”) can be mentioned, and this resin has increased polarity due to the action of an acid and increased solubility in a positive developer. It is also a resin.

Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these alkali-soluble groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  Resin (A) has a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following general formula (A).

In general formula (A),
Xa ₁ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred.
It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.

  As for content of the repeating unit which has an acid-decomposable group, 20-50 mol% is preferable with respect to all the repeating units in resin, More preferably, it is 25-45 mol%.

  Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

  The resin of component (A) preferably has a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

  Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.

  The content of the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 with respect to all repeating units in the polymer. ˜25 mol%.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  The resin of component (A) preferably has a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  As for content of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.

The resin of component (A) may further have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure.
Specifically, it is preferable that the alicyclic hydrocarbon-based acid-decomposable resin further contains a repeating unit represented by the general formula (III) that has neither a hydroxyl group nor a cyano group.

In general formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Examples of Ra include a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. Preferable monocyclic hydrocarbon groups are monocyclic hydrocarbon groups having 3 to 7 carbon atoms, and more preferable examples include a cyclopentyl group and a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino group protected with a protecting group, and the like. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and the substituent that may further have a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, an amino protected with a protecting group The group can be mentioned.

  Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The content of the repeating unit represented by the general formula (III) having neither a hydroxyl group nor a cyano group is preferably from 0 to 40 mol%, more preferably based on all repeating units in the resin (A). 0 to 20 mol%.
Specific examples of the repeating unit represented by the general formula (III) are shown below, but the present invention is not limited thereto.

  In addition to the above repeating structural unit, the resin of component (A) includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, such as resolution, heat resistance, and sensitivity. Various repeating structural units can be included for the purpose of adjusting the above.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, the performance required for the resin of component (A), in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin of component (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general resist performance required for resolving power and heat resistance. In order to adjust sensitivity and the like, it is set appropriately.

  When the resist composition of the present invention is for ArF exposure, the resin of component (A) preferably has no aromatic group from the viewpoint of transparency to ArF light.

The resin of component (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the positive photosensitive composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

The weight average molecular weight of the component (A) resin is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 as a polystyrene-converted value by the GPC method. ˜15,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

In the resist composition of the present invention, the blending amount of the component (A) resin in the entire composition is preferably 50 to 99.99% by mass, more preferably 60 to 99.0% by mass in the total solid content. .
In the present invention, the resin of component (A) may be used alone or in combination.

(B) Compound that generates acid upon irradiation with actinic ray or radiation The resist composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation (also referred to as “photoacid generator” or “(B) component”). ).
Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Among the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like. Preferably, it is an organic anion containing a carbon atom.

  Preferable organic anions include organic anions represented by the following formula.

Where
Rc ₁ represents an organic group.
It includes those having 1 to 30 carbon atoms as an organic group in rc _1, preferably substituted with optionally also an alkyl group, an aryl group, or a plurality of these, a single _{bond, -O -, - CO 2 -} , - Examples include groups linked by a linking group such as S-, -SO _3- , -SO ₂ N (Rd ₁ )-. Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group. Preferred examples of the organic group for Rc ₃ , Rc ₄ , and Rc ₅ include the same organic groups as those for Rc _1, and a perfluoroalkyl group having 1 to 4 carbon atoms is most preferred.
Rc ₃ and Rc ₄ may combine to form a ring. Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.
The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is particularly preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, when Rc ₃ and Rc ₄ are combined to form a ring, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and particularly preferable. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched oxoalkyl group, preferably an alkoxycarbonyl methyl group.
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cyclic 2-oxoalkyl group.
Linear as R ₂₀₁ to R _203, branched or cyclic 2-oxoalkyl group may preferably be a group having a 2-position> C = O in the above-described alkyl or cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Any two or more of R _1c to R _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y include a butylene group and a pentylene group.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Or a linear or branched alkyl group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, or a linear or branched pentyl group).
The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group or a cyclohexyl group).
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
The cycloalkyl group as R _x and R _y may be the same as the cycloalkyl group as R _1c to R _7c. The cycloalkyl group as R _x and R _y is preferably a cyclic 2-oxoalkyl group.
Examples of the linear, branched, or cyclic 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .
R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
R ₂₀₄ to R ₂₀₇ may have a substituent. The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZIV), (ZV), and (ZVI) can be further exemplified.

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ represents an alkyl group or an aryl group.
R ₂₀₇ and R ₂₀₈ each independently represents an alkyl group, an aryl group or an electron withdrawing group. R ₂₀₇ is preferably an aryl group.
R ₂₀₈ is preferably an electron withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  As the compound that generates an acid upon irradiation with actinic rays or radiation, compounds represented by general formulas (ZI) to (ZIII) are preferable.

  The compound (B) is preferably a compound that generates an aliphatic sulfonic acid having a fluorine atom or a benzenesulfonic acid having a fluorine atom upon irradiation with actinic rays or radiation.

  The compound (B) preferably has a triphenylsulfonium structure.

  The compound (B) is preferably a triphenylsulfonium salt compound having an alkyl group or a cycloalkyl group not substituted with fluorine in the cation moiety.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, examples of particularly preferable compounds are listed below.

A photo-acid generator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 7% by mass, based on the total solid content of the positive resist composition. It is.

As the photoacid generator, a compound (B ′) that generates an acid having a log P value of 1.5 or more and 12.0 or less upon irradiation with actinic rays or radiation is preferable.
In the present invention, the log P value of the acid generated from the compound that generates an acid upon irradiation with actinic rays or radiation is 1.5 or more and 12.0 or less, preferably 2.0 or more and 11.0 or less, more preferably It is 2.5 or more and 10.5 or less.
When the log P value is 1.5 or more and 12.0 or less, the line edge roughness is good in the pattern formation by the negative development using the negative development solution (preferably an organic solvent), and the line width is good. A pattern excellent in inner uniformity and bridge margin can be obtained. The reason for this is not clear, but it is presumed that, by setting the log P value in the above range, the dissolution of the generated acid and photoacid generator in the negative developer progressed more uniformly and smoothly. That is, by setting the log P value to 12.0 or less, the hydrophobicity of the anion portion of the generated acid and the photoacid generator is optimized to an appropriate range. As a result, in the negative development process, the generated acid and It is considered that hydrophobic aggregation between the photoacid generators was suppressed, development progressed uniformly, and the above-mentioned good performance was obtained. On the other hand, by setting the log P value to 1.5 or more, the generated acid and the photoacid generator are sufficiently dissolved in the negative developer, and as a result, the insoluble matter is prevented from being precipitated, It is considered that the above-mentioned good performance was obtained. Furthermore, by setting the log P value to 1.5 or more and 12.0 or less, a pattern having a good bridge margin can be obtained. One reason is that the development pattern is improved and the line pattern is improved. As a result, it is presumed that the connection between patterns (bridge) is reduced and the bridge margin is improved.
Even in pattern formation methods using a positive developer (usually an alkaline aqueous solution), problems of in-plane uniformity of line edge roughness and line width have been pointed out. The performance is greatly affected by the solubility at the time, and of course, when a negative developer (preferably an organic solvent) is used, the optimum range of the photoacid generator suitably used as a resist composition naturally changes. It is considered a thing.
Here, the log P value is a logarithmic value of the octanol / water partition coefficient, and is known as an important parameter representing the hydrophilicity / hydrophobicity of a molecule. As a method for obtaining the log P value of a compound, it can be roughly classified into a method for obtaining by experimental measurement and a method for obtaining by calculation.
Hereinafter, a method for calculating the logP value will be described. When the logP value is actually measured, it can be obtained by actual measurement by the method described in the following document. Moreover, when calculating logP value by calculation, the logP value calculated by calculation (it is called CLogP value) can be calculated | required by calculation using the fragment method of the following literature description, or the following commercially available software packages 1 and 2. In this specification, whenever the log P value is discussed, this C log P value is referred to, and the log P value described in the specification is the value of the “C log P value” calculated using the software package 2 below. is there.
Literature: C.I. Hansch and A.H. Leo, “Substituent Constants for Correlation Analysis in Chemistry and Biology (John Wiley & Sons, New York, 1969)
Software Package 1: MedChem Software (Release 3.54, Aug. 1991, Medicinal Chemistry Project, Pomona College, Clarmont, CA)
Software package 2: Chem Draw Ultra ver. 8.0. (April 2003, CambridgeSoft Corporation, USA)

  The compound that generates an acid having a log P value of 1.5 or more and 12.0 or less is preferably a compound having in its anion structure a group having a hydrocarbon skeleton having 2 or more carbon atoms and not fluorine-substituted. As a result, in pattern formation by negative development using a negative developer (preferably an organic solvent), line edge roughness becomes better, and line width in-plane uniformity and bridge margin become better. . More preferable examples of the compound include a compound having a group having a hydrocarbon skeleton having 3 or more carbon atoms in the anion structure, and particularly preferably fluorine having 4 or more carbon atoms in the anion structure. Examples thereof include a compound having a group having a hydrocarbon skeleton which is not substituted.

Examples of the group having a hydrocarbon skeleton having 2 or more carbon atoms not substituted with fluorine include, for example, a linear, branched or cyclic alkyl group, alkoxy group, alkoxy having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine. Examples thereof include a carbonyl group, an alkylthio group, an acylamino group, an oxoalkyl group, an alkylsulfonyloxy group, an alkylsulfonyl group, an alkylsulfonylamino group, and an alkylaminosulfonyl group. Further, it may be a divalent or trivalent linking group having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine.
The group having a hydrocarbon skeleton having 2 or more carbon atoms and not fluorine-substituted is preferably an ethyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, or n-pentyl group that is not fluorine-substituted. , Cyclopentyl group, neopentyl group, t-amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, n-hexadecyl group, n-octadecyl group, 2-ethylhexyl group, adamantyl group, norbornyl group , Alkyl groups such as menthyl group, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group,
Non-fluorinated ethoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, cyclopentyloxy group, neopentyloxy group, t-amyloxy group, n-hexyloxy Group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, n-hexadecyloxy group, n-octadecyloxy group, 2-ethylhexyloxy group, adamantyloxy group, norbornyloxy group, menthyloxy Groups, alkoxy groups such as adamantylmethoxy group, adamantylethoxy group, cyclohexylethoxy group,
An alkoxycarbonyl group in which the alkoxy group is linked to a carbonyl group;
An alkylthio group in which the oxygen atom of the alkoxy group is replaced with a sulfur atom,
An oxoalkyl group substituted with an oxo group at any position of the alkyl group,
An acylamino group in which the alkyl group is linked to a —C (═O) N (Rx ₁ ) — group (wherein Rx ₁ represents a hydrogen atom or an alkyl group);
Alkylsulfonyloxy group which the alkyl group is linked to -SO 2 _O-group,
The alkyl group is -SO 2 _- alkylsulfonyl group linked with groups,
The alkyl group is _-SO 2 N (Rx ₁₎ - alkylsulfonylamino group linked with groups,
_{(Rx 1) (Rx 2)} NSO 2 - alkylaminosulfonyl group represented by (wherein, Rx ₂ represents an alkyl group not substituted with fluorine carbon number of 2 or more, Rx ₁ and Rx ₂ are bonded And a ring structure having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine may be formed).

  The hydrocarbon skeleton having 2 or more carbon atoms and not fluorine-substituted may be present at any position in the molecule, but is preferably at the molecular end.

  As the compound that has a group having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine in its anion structure and generates an acid having a log P value of 1.5 or more and 12.0 or less, the following acids are generated. However, the present invention is not limited to these.

  As another preferred form of the compound (B ′) that generates an acid having a log P value of 1.5 or more and 12.0 or less, a compound that generates a sulfonic acid represented by the following general formula (I) or (I ′) Is mentioned.

In general formulas (I) and (I ′),
A ₁ represents a divalent linking group.
A ₂ and A ₃ each independently represents a single bond, an oxygen atom or —N (Rxb) —.
Rxb represents a hydrogen atom, an aryl group, an alkyl group or a cycloalkyl group.
A ₄ represents a single bond or —C (═O) —.
Ra represents a hydrogen atom or an organic group.
n represents 2 or 3.
Rb represents an n-valent linking group.
When A ₃ is —N (Rxb) —, Ra and Rxb or Rb and Rxb may combine to form a ring.

The divalent linking group as A ₁ is preferably an organic group having 1 to 20 carbon atoms, more preferably an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably. C3-4). The alkylene chain may have a linking group such as an oxygen atom, a sulfur atom, a —C (═O) — group or an ester group.
The divalent linking group as A ₁ is more preferably an alkylene group substituted with a fluorine atom, and particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with a fluorine atom. In the case of an alkylene group substituted with a fluorine atom, the carbon atom bonded to the —SO ₃ H group preferably has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are most preferable.

  The aryl group in Rxb may have a substituent, and preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group and a naphthyl group.

  The alkyl group as Rxb may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom in the alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.

  Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

  The cycloalkyl group as Rxb may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

Ra represents a hydrogen atom or a monovalent organic group.
The monovalent organic group as Ra preferably has 1 to 20 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

  The alkyl group, cycloalkyl group or aryl group as Ra is the same as those exemplified as Rxb.

  The aralkyl group as Ra is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

  Examples of the alkenyl group as Ra include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rxb.

The n-valent linking group as Rb preferably has 1 to 20 carbon atoms. When n = 2 in the general formula (I ′), the divalent linking group as Rb is, for example, an alkylene group (preferably having 1 to 20 carbon atoms) or an arylene group (preferably having 6 to 10 carbon atoms). , An aralkylene group (preferably having a carbon number of 7 to 13) and an alkenylene group (preferably having a carbon number of 2 to 12). These may have a substituent.
Examples of the trivalent linking group as Rb when n = 3 include a trivalent group excluding any hydrogen atom of the divalent linking group.

When A ₃ is —N (Rxb) —, the ring formed by combining Ra and Rxb or Rb and Rxb is preferably a ring having 4 to 10 carbon atoms containing a nitrogen atom, and may be monocyclic or polycyclic . Moreover, you may have an oxygen atom in the ring.

  Examples of the substituent that each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), and an aryl group (preferably having a carbon number). 6-14), an alkoxy group (preferably having 1 to 20 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 20 carbon atoms), and the like. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20).

  The sulfonic acids of the general formulas (I) and (I ′) are preferably sulfonic acids represented by the following general formulas (IA) to (IC) and (I′A) to (I′C).

In general formulas (IA) to (IC) and (I′A) to (I′C),
Ra ′ has the same meaning as Ra in formula (I).
Rb and n are synonymous with Rb and n in the general formula (I ′).
Ra ″ represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group.
Rx ′ is synonymous with Rxb in the general formulas (I) and (I ′).
n1 represents an integer of 1 to 10.
n2 represents an integer of 0 to 10.
A ₅ represents a single bond, —O—, an alkylene group, a cycloalkylene group or an arylene group.

The alkylene group or cycloalkylene group as A ₅ is preferably an alkylene group or cycloalkylene group which is not fluorine-substituted.
In the general formula (IA), Ra ′ and Rx ′ are preferably bonded to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The ring to be formed preferably has 4 to 20 carbon atoms, may be monocyclic or polycyclic, and may contain an oxygen atom in the ring.
Examples of the alkyl group, aryl group, aralkyl group or alkenyl group as Ra ″ include the same as the alkyl group, aryl group, aralkyl group or alkenyl group as Ra.
n1 + n2 is preferably 2-8, more preferably 2-6.

  Preferred specific examples of the sulfonic acid represented by the general formula (I) or (I ′) are shown below, but the present invention is not limited thereto.

  Among these, a compound having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine in the anion structure is more preferable.

  Still another preferred embodiment of the compound (B ′) that generates an acid having a log P value of 1.5 or more and 12.0 or less includes a compound that generates a sulfonic acid represented by the following general formula (II).

In general formula (II):
Rf represents a fluorine atom or an organic group having a fluorine atom.
R _a1 and R _b1 each independently represents an organic group.
Ar represents an aromatic group.
X _{is, -SO -, - SO 2 -} , - S- or an -O-.
l ′ represents an integer of 0 to 6.
m ′ represents an integer of 0 to 5.
n ′ represents an integer of 0 to 5.

In the general formula (II), examples of the organic group represented by R _a1 and R _b1 include an alkyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, aralkyl group, aralkyloxy group, cycloalkoxy group, and alkoxycarbonyl. Group, aryloxycarbonyl group, acyloxy group, alkylthio group, arylthio group, acyl group, acylamino group, alkenyl group, alkenyloxy group, arylcarbonyloxy group, alkylcarbonyloxy group, alkylaminocarbonyl group, alkylcarbonylamino group, alkyl A silyloxy group, a cyano group, etc. can be mentioned. A plurality of these organic groups may be linked by a single bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a urea bond, or the like. The organic group of R _a1 and R _b1 preferably has 2 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 30 carbon atoms, and particularly preferably 8 to 8 carbon atoms. 24.

The alkyl group in the organic group of R _a1 and R _b1 is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples include sec-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. The alkyl group may have a substituent. Preferred examples of the substituent for the alkyl group include an alkoxy group, a cycloalkyl group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The in the aryl group in the organic group of R _a1 and R _b1, a phenyl group, a tolyl group, a mesityl group, and naphthyl group. Preferred substituents for the aryl group include, for example, alkyl groups, cycloalkyl groups, alkoxy groups, acyloxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, halogen atoms, aryl groups, alkoxycarbonyl groups, chlorines. An atom, a bromine atom, an iodine atom, a hydroxyl group, a carboxyl group, and a cyano group are mentioned.

The cycloalkyl group in the organic group of R _a1 and R _b1 is preferably a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl. Group, adamantyl group and the like. The cycloalkyl group may have a substituent. Preferred examples of the substituent for the cycloalkyl group include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkoxy group in the organic group of R _a1 and R _b1 is preferably a linear or branched alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and an n-butoxy group. , Isobutoxy group, sec-butoxy group, t-butoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like. The alkoxy group may have a substituent. Preferred examples of the substituent for the alkoxy group include an alkoxy group, an aryl group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group, a cycloalkoxy group, a siloxane group, a hydroxyl group, and a carboxyl group. be able to.

The aryloxy group in the organic group of R _a1 and R _b1 is preferably an aryloxy group having 6 to 20 carbon atoms, and examples thereof include a phenoxy group. The aryloxy group may have a substituent. Preferred substituents for the aryloxy group include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a chlorine atom, a bromine atom, an iodine atom, and an alkoxycarbonyl group. , A cyano group, a hydroxyl group, and a carboxyl group.

The aralkyl group in the organic group of R _a1 and R _b1 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group and a phenethyl group. The aralkyl group may have a substituent. Preferred substituents for the aralkyl group include, for example, alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, chlorine atoms, bromine atoms, iodine atoms, alkoxycarbonyl groups, A cyano group, a hydroxyl group, and a carboxyl group can be mentioned.

  The aralkyloxy group is preferably an aralkyloxy group having 6 to 20 carbon atoms, and examples thereof include aralkyloxy groups such as benzyloxy group and phenethyl group. The aralkyloxy group may have a substituent. Preferred substituents for the aralkyloxy group include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a chlorine atom, a bromine atom, an iodine atom, and an alkoxycarbonyl group. , A cyano group, a hydroxyl group, and a carboxyl group.

The cycloalkoxy group in the organic group of R _a1 and R _b1 is preferably a monocyclic or polycyclic cycloalkoxy group having 3 to 30 carbon atoms, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group. Group, norbornyloxy group, menthyloxy group, adamantyloxy group and the like. The cycloalkoxy group may have a substituent. Preferred examples of the substituent for the cycloalkoxy group include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkoxycarbonyl group in the organic group of R _a1 and R _b1 is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, or a dodecyloxycarbonyl group. Groups and the like. The alkoxycarbonyl group may have a substituent. Preferred examples of the substituent for the alkoxycarbonyl group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The aryloxycarbonyl group in the organic group of R _a1 and R _b1 is preferably an aryloxycarbonyl group having 6 to 20 carbon atoms, and examples thereof include a phenoxycarbonyl group. The aryloxycarbonyl group may have a substituent. Preferred substituents for the aryloxycarbonyl group include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, Examples thereof include a carboxyl group, an alkoxycarbonyl group, and a cyano group.

The acyloxy group in the organic group of R _a1 and R _b1 is preferably an acyloxy group having 1 to 30 carbon atoms, such as an acetoxy group, a methylbutinoyloxy group, a methyldecinoyloxy group, a propionyloxy group, a butyryloxy group, A valeryloxy group, a palmitoyloxy group, a benzoyloxy group, etc. can be mentioned. The acyloxy group may have a substituent. Preferred substituents for the acyloxy group include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group. , An alkoxycarbonyl group, and a cyano group.

The alkylthio group in the organic group of R _a1 and R _b1 is preferably an alkylthio group having 1 to 30 carbon atoms, such as methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group. , T-butylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, and the like. The alkylthio group may have a substituent. Preferred examples of the substituent for the alkylthio group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The arylthio group in the organic group of R _a1 and R _b1 is preferably an arylthio group having 6 to 20 carbon atoms, and examples thereof include a phenylthio group. The arylthio group may have a substituent. Preferred substituents for the arylthio group include, for example, alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, carboxyl groups. , Alkoxycarbonyl group, cyano group and the like.

The acyl group in the organic group of R _a1 and R _b1 is preferably an acyl group having 1 to 30 carbon atoms, such as acetyl group, propionyl group, pivaloyl group, butyryl group, valeryl group, palmitoyl group, benzoyl group, etc. Can be mentioned. The acyl group may have a substituent. Preferred substituents for the acyl group include, for example, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group. , An alkoxycarbonyl group, and a cyano group.

The acylamino group in the organic group of R _a1 and R _b1 is preferably an acylamino group having 1 to 30 carbon atoms, and examples thereof include an acetylamino group, a propionylamino group, a pivaloylamino group, a butyrylamino group, and a benzoylamino group. it can. The acylamino group may have a substituent. Preferred substituents for the acylamino group include, for example, alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, carboxyl groups. , An alkoxycarbonyl group, and a cyano group.

The alkenyl group in the organic group of R _a1 and R _b1 is preferably an alkenyl group having 1 to 30 carbon atoms, and examples thereof include a vinyl group, a propenyl group, and a butenyl group. The alkenyl group may have a substituent. Preferred examples of the alkenyl group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkenyloxy group in the organic group of R _a1 and R _b1 is preferably an alkenyloxy group having 1 to 30 carbon atoms, and examples thereof include a vinyloxy group, a propenyloxy group, and a butenyloxy group. The alkenyloxy group may have a substituent. Preferred examples of the substituent for the alkenyloxy group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The arylcarbonyloxy group in the organic group of R _a1 and R _b1 is preferably an arylcarbonyloxy group having 6 to 20 carbon atoms, and examples thereof include a phenylcarbonyloxy group. The arylcarbonyloxy group may have a substituent. Preferred examples of the substituent for the arylcarbonyloxy group include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, an alkoxycarbonyl group, a cyano group, a chlorine atom, and a bromine. An atom, an iodine atom, a hydroxyl group, a carboxyl group, etc. can be mentioned.

The alkylcarbonyloxy group in the organic group of R _a1 and R _b1 is preferably an alkylcarbonyloxy group having 1 to 30 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, or a butylcarbonyloxy group. Groups and the like. The alkylcarbonyloxy group may have a substituent. Preferred examples of the substituent for the alkylcarbonyloxy group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkylaminocarbonyl group in the organic group of R _a1 and R _b1 is preferably an alkylaminocarbonyl group having 1 to 30 carbon atoms, such as a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group, or a butylaminocarbonyl group. Groups and the like. The alkylaminocarbonyl group may have a substituent. Preferred examples of the substituent for the alkylaminocarbonyl group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkylcarbonylamino group in the organic group of R _a1 and R _b1 is preferably an alkylcarbonylamino group having 1 to 30 carbon atoms, such as a methylcarbonylamino group, an ethylcarbonylamino group, a propylcarbonylamino group, or a butylcarbonylamino group. Groups and the like. The alkylcarbonylamino group may have a substituent. Preferred examples of the substituent for the alkylcarbonylamino group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

The alkylsilyloxy group in the organic group of R _a1 and R _b1 is preferably an alkylsilyloxy group having 1 to 30 carbon atoms, and examples thereof include a trimethylsilyloxy group and a t-butyldimethylsilyloxy group. The alkylsilyloxy group may have a substituent. Preferred examples of the substituent for the alkylsilyloxy group include an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a carboxyl group.

  These alkyl groups, cycloalkyl groups, and alkoxy groups, aralkyloxy groups, cycloalkoxy groups, alkoxycarbonyl groups, acyloxy groups, alkylthio groups, acyl groups, and alkyl groups possessed by acylamino groups, cycloalkyl groups, The alkyl chain may have one or more linking groups such as an oxygen atom, a sulfur atom, and an ester group.

Preferred examples of R _a1 and R _b1 include an alkyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, aralkyl group, aralkyloxy group, cycloalkoxy group, alkylthio group, arylthio group, acyl group, acylamino group, alkenyl. Group, alkenyloxy group, arylcarbonyloxy group, alkylcarbonyloxy group, alkylcarbonylamino group, alkylsilyloxy group. More preferable R _a1 and R _b1 include an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkyloxy group, a cycloalkoxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, An alkenyl group, an alkenyloxy group, an arylcarbonyloxy group, and an alkylcarbonylamino group, more preferably an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkyloxy group, a cycloalkoxy group, An acylamino group, an alkenyl group, an alkenyloxy group, an arylcarbonyloxy group, and an alkylcarbonylamino group;

When l ′ and n ′ are integers of 2 or more, a plurality of R _a1 and R _b1 may be the same or different.

Rf represents a fluorine atom or an organic group having a fluorine atom, and examples of the organic group having a fluorine atom include those in which a part or all of the hydrogen atoms of the organic group in R _a1 and R _b1 are substituted by a fluorine atom. It is done. When m ′ is an integer of 2 or more, the plurality of Rf may be the same or different.

The sum of the carbon number of Rf, R _a1 and R _b1 is preferably 4 to 34 carbon atoms, more preferably 6 to 30 carbon atoms, and still more preferably 8 to 24 carbon atoms. By adjusting the carbon number of Rf, R _a1 and R _b1, the acid diffusivity can be adjusted, and the resolution is improved.

  The aromatic group of Ar is preferably an aromatic group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The aromatic group may further have a substituent. Preferable further substituents of the aromatic group include, for example, nitro group, sulfonylamino group, chlorine atom, bromine atom, iodine atom, carboxyl group and the like.

l ′ is preferably 0 to 3, more preferably 0 to 2, and further preferably 1 or 2.
n ′ is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.
m ′ is preferably 2 to 5, more preferably 3 or 4, and still more preferably 4.

The sulfonic acid represented by the general formula (II) is preferably represented by the following general formula (IIa), more preferably represented by the general formula (IIb), and represented by the general formula (IIc). Even more preferred. _{Wherein, R a1, Rf, X,} l ', m', n ' is in the general formula _{(II) R a1, Rf,} X, l', m ', n' is synonymous with. R is the same as R _a1 .

Hereinafter, preferred specific examples of the sulfonic acid represented by the general formula (II) are listed, but the present invention is not limited thereto.

  Among these, a compound having a hydrocarbon skeleton having 2 or more carbon atoms and not substituted with fluorine in the anion structure is more preferable.

  The compound that generates the sulfonic acid represented by the general formula (I), (I ′) or (II) upon irradiation with actinic rays or radiation is represented by the general formula (I), (I ′) or (II). Preferred is one selected from sulfonium salt compounds or iodonium salt compounds of sulfonic acids, or one selected from ester compounds of sulfonic acids represented by (I), (I ′) or (II), more preferably Are compounds represented by general formulas (B1) to (B5).

In the general formula (B1), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a sulfonate anion from which a hydrogen atom of the sulfonic acid (—SO ₃ H) of the general formula (I), (I ′) or (II) is removed.
Examples of the organic group as R _201, R ₂₀₂ and R ₂₀₃ are the same as those described above in the general formula (ZI) aryl group of R _201, R ₂₀₂ and R _203, exemplary alkyl group or a cycloalkyl group .

In the general formula (B2), _R204 and _R205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
X ⁻ represents a sulfonate anion from which a hydrogen atom of the sulfonic acid (—SO ₃ H) of the general formula (I), (I ′) or (II) is removed.

R ₂₀₄ and R _{205 in the} general formula (B2) are the same as those described as R ₂₀₄ and R ₂₀₅ in the general formula (ZII).

In the general formula (B3), A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.
X ₁ represents a monovalent group from which a hydrogen atom of the sulfonic acid (—SO ₃ H) of the general formula (I), (I ′) or (II) is removed.

In the general formula (B4), R ₂₀₈ represents a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group.
R ₂₀₉ represents an alkyl group, a cyano group, an oxoalkyl group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group or a cyano group.
X ₁ represents a monovalent group from which a hydrogen atom of the sulfonic acid (—SO ₃ H) of the general formula (I), (I ′) or (II) is removed.

In the general formula (B5), R ₂₁₀ and R ₂₁₁ each independently represent a hydrogen atom, an alkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group, a nitro group or a cyano group. is there.
_R212 represents a hydrogen atom, an alkyl group, a cyano group or an alkoxycarbonyl group.
X ₁ represents a monovalent group from which a hydrogen atom of the sulfonic acid (—SO ₃ H) of the general formula (I), (I ′) or (II) is removed.

  Preferably, it is a compound represented by general formula (B1), More preferably, they are compounds (B1a)-(B1c).

  The compound (B) preferably has a triphenylsulfonium structure.

  The compound (B) is preferably a triphenylsulfonium salt compound having an alkyl group or a cycloalkyl group not substituted with fluorine in the cation moiety.

  Preferred examples of the compound (B ′) that generates an acid having a log P value of 1.5 or more and 12.0 or less upon irradiation with actinic rays or radiation are given below, but the present invention is not limited thereto. Is not to be done.

When using in combination of 2 or more types, you may use together a compound (B ') and another acid generator.
When two or more kinds are used in combination, the amount of the acid generator used is usually 99/1 to 20/80, preferably 99/1 to 40 / in molar ratio (compound (B ′) / other acid generator). 60, more preferably 99/1 to 50/50.

  Examples of such acid generators that can be used in combination include photocation polymerization photoinitiators, photoradical polymerization photoinitiators, dye photodecolorants, photochromic agents, and actives used in microresists. Known compounds that generate an acid upon irradiation with light or radiation and mixtures thereof can be appropriately selected and used.

(C) Solvent Solvents that can be used when preparing the resist composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Organic solvents such as acid alkyl, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, etc. be able to.
Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

(D) Resin having at least one of fluorine atom and silicon atom The resist composition of the present invention preferably contains a resin (D) having at least one of a fluorine atom and a silicon atom.
The fluorine atom or silicon atom in the resin (D) may be contained in the main chain of the resin or may be substituted with a side chain.

The resin (D) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

  Specific examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom are shown below, but the present invention is not limited thereto.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ and at least one of R _{65 to} R ₆₈ are fluorine atoms or at least one hydrogen atom is a fluorine atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms) substituted with. R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoroethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group,
Examples include perfluoro (trimethyl) hexyl group, 2,2,3,3-tetrafluorocyclobutyl group, and perfluorocyclohexyl group. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

The resin (D) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear alkyl group (preferably having 1 to 20 carbon atoms), a branched alkyl group or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a ureylene group or a urea group, or a combination of two or more groups. Can be mentioned.
n represents an integer of 1 to 5.

  Examples of the resin (D) include resins having at least one selected from the group of repeating units represented by the following general formulas (CI) to (CV).

In the general formulas (CI) to (CV),
R _{1 to} R ₃ are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) or a linear or branched fluorinated alkyl group (preferably having 1 carbon atom). ~ 4).
W _{1 to} W ₂ represent an organic group having at least one of a fluorine atom and a silicon atom.
R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) or a linear or branched fluorinated alkyl group (preferably having 1 carbon atom). ~ 4). However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.
R ₈ represents a hydrogen atom or a linear or branched alkyl group (preferably having 1 to 4 carbon atoms).
R ₉ represents a linear or branched alkyl group (preferably having 1 to 4 carbon atoms) or a linear or branched fluorinated alkyl group (preferably having 1 to 4 carbon atoms).
L < ₁ > -L < ₂ > represents a single bond or a bivalent coupling group, and is the same as said L < ₃ > -L < ₅ >.
Q represents a monocyclic or polycyclic cyclic aliphatic group. That is, it represents an atomic group that contains two bonded carbon atoms (C—C) and forms an alicyclic structure.
R ₃₀ and R ₃₁ each independently represents a hydrogen atom or a fluorine atom.
R ₃₂ and R ₃₃ each independently represents an alkyl group, a cycloalkyl group, a fluorinated alkyl group or a fluorinated cycloalkyl group.
However, the repeating unit represented by formula (CV) has at least one fluorine atom in at least one of R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ .

  The resin (D) preferably has a repeating unit represented by the general formula (CI), and further has a repeating unit represented by the following general formulas (C-Ia) to (C-Id). preferable.

In the general formulas (C-Ia) to (C-Id),
R ₁₀ and R ₁₁ are a hydrogen atom, a fluorine atom, a linear or branched alkyl group (preferably having 1 to 4 carbon atoms), or a linear or branched fluorinated alkyl group (preferably having 1 to 4 carbon atoms). Represents.
W _{3 to} W ₆ represent an organic group having at least one of a fluorine atom and a silicon atom.

When W _{1 to} W ₆ are an organic group having a fluorine atom, a fluorinated linear or branched alkyl group (preferably having a carbon number of 1 to 20), a fluorinated cycloalkyl group (preferably having a carbon number) 3-20) or a fluorinated linear, branched or cyclic alkyl ether group (preferably having 1 to 20 carbon atoms).

Examples of the fluorinated alkyl group for W _{1 to} W ₆ include trifluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, heptafluorobutyl group, heptafluoroisopropyl group, octafluoro Examples thereof include an isobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, a perfluoroisopentyl group, a perfluorooctyl group, and a perfluoro (trimethyl) hexyl group.

When W _{1 to} W ₆ are organic groups having a silicon atom, it is preferably a group having an alkylsilyl structure or a cyclic siloxane structure. Specific examples include groups represented by the general formulas (CS-1) to (CS-3).

Hereinafter, although the specific example of the repeating unit represented by general formula (CI) is shown, this invention is not limited to this. In the formula, X represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

The resin (D) is preferably any resin selected from the following (D-1) to (D-6).
(D-1) A resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a resin having only a repeating unit (a).
(D-2) A resin having a repeating unit (b) having a trialkylsilyl group or a group having a cyclic siloxane structure, more preferably a resin having only a repeating unit (b).
(D-3) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 to 4 carbon atoms) 20) a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms). A resin having a repeating unit (a) and a repeating unit (c).
(D-4) a repeating unit (b) having a trialkylsilyl group or a group having a cyclic siloxane structure, a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 to 20 carbon atoms) ), A branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms) and a repeating unit (c). Resin, more preferably a copolymer resin of repeating unit (b) and repeating unit (c).
(D-5) a resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms) and a repeating unit (b) having a trialkylsilyl group or a group having a cyclic siloxane structure; Preferably, a copolymer resin of repeating unit (a) and repeating unit (b).
(D-6) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a repeating unit (b) having a trialkylsilyl group or a group having a cyclic siloxane structure, and a branched alkyl group (Preferably 4 to 20 carbon atoms), cycloalkyl group (preferably 4 to 20 carbon atoms), branched alkenyl group (preferably 4 to 20 carbon atoms), cycloalkenyl group (preferably 4 to 20 carbon atoms) or A resin having a repeating unit (c) having an aryl group (preferably having 4 to 20 carbon atoms), more preferably a copolymer resin of the repeating unit (a), the repeating unit (b) and the repeating unit (c).
As the repeating unit (c) having a branched alkyl group, a cycloalkyl group, a branched alkenyl group, a cycloalkenyl group, or an aryl group in the resins (D-3), (D-4), and (D-6) In view of hydrophilicity / hydrophobicity, interaction, etc., an appropriate functional group can be introduced, but from the viewpoints of immersion liquid followability and receding contact angle, a functional group having no polar group is preferred. .
In the resins (D-3), (D-4), and (D-6), a repeating unit (a) having a fluoroalkyl group and / or a repeating unit having a trialkylsilyl group or a group having a cyclic siloxane structure (B) is preferably 20 to 99 mol%.

  The resin (D) is preferably a resin having a repeating unit represented by the following general formula (Ia).

In general formula (Ia):
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₁ represents an alkyl group.
R ₂ represents a hydrogen atom or an alkyl group.

In general formula (Ia), the alkyl group in which at least one hydrogen atom of Rf is substituted with a fluorine atom preferably has 1 to 3 carbon atoms, and more preferably a trifluoromethyl group.
The alkyl group for R ₁ is preferably a linear or branched alkyl group having 3 to 10 carbon atoms, and more preferably a branched alkyl group having 3 to 10 carbon atoms.
R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 10 carbon atoms.

  Hereinafter, although the specific example of the repeating unit represented by general formula (Ia) is given, this invention is not limited to this.

  The repeating unit represented by the general formula (Ia) can be formed by polymerizing a compound represented by the following general formula (If).

In general formula (If),
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₁ represents an alkyl group.
R ₂ represents a hydrogen atom or an alkyl group.

In the general formula (the If), Rf, R ₁ and R ₂ are in the general formula (Ia), Rf, R ₁ and R ₂ synonymous.
As the compound represented by the general formula (If), a commercially available product may be used, or a synthesized product may be used. In the case of synthesis, 2-trifluoromethylmethacrylic acid can be obtained by acidification and then esterification.

  The resin (D) having a repeating unit represented by the general formula (Ia) preferably further has a repeating unit represented by the following general formula (IIIF).

In general formula (IIIF):
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, or a group having a cyclic siloxane structure.
L ₆ represents a single bond or a divalent linking group.

In the general formula (IIIF), the alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.
The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.
The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

  Hereinafter, although the specific example of resin (D) which has a repeating unit represented by general formula (Ia) is given, this invention is not limited to this.

  The resin (D) is preferably a resin having a repeating unit represented by the following general formula (IIF) and a repeating unit represented by the following general formula (IIIF).

In general formulas (IIF) and (IIIF),
Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or a group formed by combining two or more thereof.
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, a group having a cyclic siloxane structure, or a group formed by combining two or more thereof.
L ₆ represents a single bond or a divalent linking group.
m and n represent the ratio of repeating units, and 0 <m <100 and 0 <n <100.

Rf in the general formula (IIF) is the same as Rf in the general formula (Ia).
The alkyl group of R ₃ and R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The trialkylsilyl group for R ₄ is preferably a trialkylsilyl group having 3 to 20 carbon atoms.
The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.
The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, and trialkylsilyl group of R ₃ and R ₄ can introduce a functional group, but have a polar group from the viewpoint of immersion liquid followability. The functional group is preferably not substituted, and more preferably unsubstituted.
L ₆ is preferably a single bond, a methylene group, an ethylene group or an ether group.
m = 30 to 70 and n = 30 to 70 are preferable, and m = 40 to 60 and n = 40 to 60 are more preferable.

  Hereinafter, specific examples of the resin (D) having the repeating unit represented by the general formula (IIF) and the repeating unit represented by the general formula (IIIF) will be described, but the present invention is not limited thereto. .

  Resin (D) may have a repeating unit represented by the following general formula (VIII).

In general formula (VIII):
Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  The resin (D) is preferably solid at room temperature (25 ° C.). Furthermore, it is preferable that glass transition temperature (Tg) is 50-200 degreeC, and 80-160 degreeC is more preferable.

Being solid at 25 ° C. means that the melting point is 25 ° C. or higher.
The glass transition temperature (Tg) can be measured by differential scanning calorimeter. For example, the specific volume changed when the sample was heated once, cooled and then heated again at 5 ° C./min. It can be measured by analyzing the value.

  The resin (D) is preferably stable to an acid and insoluble in an alkaline developer.

Resin (D) is decomposed by the action of (x) an alkali-soluble group, (y) an alkali (alkaline developer), a group that increases the solubility in the alkali developer and (z) an acid, From the viewpoint of the followability of the immersion liquid, it is preferable not to have a group that increases the solubility in the developer.
The total amount of repeating units having an alkali-soluble group in the resin (D) or a group whose solubility in a developer is increased by the action of an acid or an alkali is preferably 20 with respect to all the repeating units constituting the resin (D). It is not more than mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5 mol%.
In addition, unlike the surfactant generally used in resists, the resin (D) does not have an ionic bond or a hydrophilic group such as a (poly (oxyalkylene)) group. When the resin (D) has a hydrophilic polar group, the followability of immersion water tends to decrease. Therefore, it is more preferable that the resin (D) does not have a polar group selected from a hydroxyl group, an alkylene glycol, and a sulfone group. In addition, it is preferable not to have an ether group bonded to a carbon atom of the main chain through a linking group because hydrophilicity increases and immersion liquid followability deteriorates. On the other hand, an ether group directly bonded to a carbon atom of the main chain as shown by the general formula (IIIF) is preferable because it may express a hydrophobic group.

  (X) Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, and (alkylsulfonyl). (Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkyl And a group having a sulfonyl) methylene group.

  (Y) Examples of the group that decomposes by the action of an alkali (alkaline developer) and increases the solubility in the alkali developer include a lactone group, an ester group, a sulfonamide group, an acid anhydride, and an acid imide group. Can be mentioned.

  (Z) Examples of the group that decomposes by the action of an acid and increases the solubility in a developer include the same groups as the acid-decomposable groups in the resin (A).

  However, the repeating unit represented by the following general formula (pA-c) has no or very little decomposability due to the action of acid as compared with the acid-decomposable group of the resin (A), and is substantially non-acid-decomposable. Considered equivalent to gender.

In the general formula (pA-c),
Rp ₂ represents a hydrocarbon group having a tertiary carbon atom bonded to the oxygen atom in the formula.

  When the resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (D). Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mass% in resin (D), and it is more preferable that it is 20-100 mass%.

  When resin (D) has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of resin (D). Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in resin (D), and it is more preferable that it is 30-100 mass%.

  The weight average molecular weight in terms of standard polystyrene of the resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000, and particularly preferably. Is 3,000 to 15,000.

  The resin (D) preferably has a residual monomer amount of 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 in terms of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of ~ 1.5.

  The amount of the resin (D) added in the resist composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the resist composition. preferable. Furthermore, it is preferable that it is 0.1-5 mass%, More preferably, it is 0.2-3.0 mass%, More preferably, it is 0.3-2.0 mass%.

  Resin (D), like resin (A), naturally has few impurities such as metals, but the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by mass or the like by HPLC. It is preferable that not only the sensitivity, resolution, process stability, pattern shape and the like as a resist can be further improved, but also a resist having no change over time such as foreign matter in liquid and sensitivity can be obtained.

  As the resin (D), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer type and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of the monomer type and the polymerization initiator is added to the heating solvent over 1 to 10 hours. Examples thereof include a dropping polymerization method which is added dropwise, and a dropping polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide. Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred polymerization initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. A chain transfer agent can also be used as needed. The concentration of solutes such as monomers, polymerization initiators and chain transfer agents in the reaction solution is usually 5 to 50% by mass, preferably 20 to 50% by mass, and more preferably 30 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer. For example, hydrocarbon (pentane, hexane, Aliphatic hydrocarbons such as heptane and octane; Cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.) Halogenated aliphatic hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, diisopropyl ether, dimethoxyethane) Chain A Cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols ( (Methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.), water, a mixed solvent containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable. In such a solvent containing at least alcohol, the ratio of alcohol (particularly methanol, etc.) to other solvent (eg, ester such as ethyl acetate, ether such as tetrahydrofuran) is, for example, the former / the latter (volume ratio; 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = 50/50 About 97/3.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The nozzle diameter at the time of supplying the polymer solution to the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mmφ or less (for example, 0.2 to 4 mmφ). Moreover, the supply speed (dropping speed) of the polymer solution into the poor solvent is, for example, about 0.1 to 10 m / second, preferably about 0.3 to 5 m / second, as the linear speed.

  The precipitation or reprecipitation operation is preferably performed with stirring. As a stirring blade used for stirring, for example, a desk turbine, a fan turbine (including a paddle), a curved blade turbine, an arrow blade turbine, a fiddler type, a bull margin type, an angled blade fan turbine, a propeller, a multistage type, an anchor type (or Horseshoe type), gate type, double ribbon, screw, etc. can be used. Stirring is preferably further performed for 10 minutes or more, particularly 20 minutes or more after the supply of the polymer solution. When the stirring time is short, the monomer content in the polymer particles may not be sufficiently reduced. Further, the polymer solution and the poor solvent can be mixed and stirred using a line mixer instead of the stirring blade.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

The resin may be once deposited and separated, and then dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent.
That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
The solvent used in the preparation of the resin solution A can be the same solvent as the solvent that dissolves the monomer in the polymerization reaction, and may be the same as or different from the solvent used in the polymerization reaction.

(E) Basic compound The resist composition of the present invention preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

  Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4. 0] Undecaker 7-ene and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl). Examples include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure turns into carboxylate, For example, an acetate, an adamantane 1-carboxylate, a perfluoroalkyl carboxylate etc. are mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. -CH ₂ CH ₂ O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or -CH ₂ CH ₂ CH ₂ O- structure is preferred.
Specific examples of the amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group include US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in [0066] are not limited thereto.
These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally based on solid content of a resist composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(F) Surfactant The resist composition of the present invention preferably further contains a surfactant, and fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, fluorine atom and It is more preferable to contain any one or two or more of surfactants having both silicon atoms.

When the resist composition of the present invention contains a surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes.
Examples of such surfactants include those described in US Patent Application Publication No. 2008/0187860 [0598] to [0602].

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the resist composition (excluding the solvent).

(G) Onium carboxylate The resist composition in the present invention may contain an onium carboxylate. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition. %.

(H) Other additives The resist composition of the present invention further promotes solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and developers as necessary. The compound to be made (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The solid content concentration of the resist composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. . By setting the solid content concentration within the above range, it is possible to uniformly apply the resist solution on the substrate and to form a resist pattern having excellent line edge roughness. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the resist composition.

  In the pattern forming method of the present invention, a step of forming a film with a resin composition whose solubility in a negative developer is reduced by irradiation with actinic rays or radiation, a step of exposing the film, a step of heating, and a positive The step of mold development can be performed by a generally known method.

The light source wavelength limit is not used for the exposure apparatus in the present invention, KrF excimer laser wavelength (248 nm), ArF excimer laser wavelength and (193 nm) F ₂ can be applied to excimer laser wavelength (157 nm) or the like.

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention.
The immersion exposure method is a technology for filling and exposing a projection lens and a sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) as a technique for increasing the resolving power.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The resolution and the depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

  When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

  On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process such as the photolithographic lithography process can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

When performing positive development, an alkali developer is preferably used.
Examples of the alkaline developer used for positive development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetramethylammonium hydroxide Alkaline aqueous solutions such as quaternary ammonium salts such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, a 2.38% aqueous solution of tetramethylammonium hydroxide is desirable.

  As the rinsing liquid in the rinsing treatment performed after the positive development, pure water can be used and an appropriate amount of a surfactant can be added.

When performing negative development, it is preferable to use an organic developer containing an organic solvent.
As an organic developer that can be used in negative development, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used. .
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. And methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, and the like.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- Examples thereof include ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, etc. It can be mentioned call ether solvents or the like.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water.
In particular, the negative developer is preferably a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. These solvents are suitable for generating a dissolution contrast corresponding to the change in polarity of the resin of the present application due to the action of an acid.

The vapor pressure of the negative developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the negative developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl Alcohol solvents such as alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, Glycol solvents such as diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, etc. Glycol ether solvents, ether solvents such as tetrahydrofuran, N-methyl-2-pi Pyrrolidone, N, N- dimethylacetamide, N, N-dimethylformamide amide solvents, toluene, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ester solvents such as ethyl lactate, butyl lactate, propyl lactate, n-butyl alcohol, sec-butyl alcohol Alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol and other alcohol solvents, ethylene glycol, diethylene glycol, triethylene glycol and other glycol solvents, Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, N-methyl-2-pyrrolidone N, N-dimethylacetamide, N, N-dimethylformamide amide solvents, xylene and other aromatic hydrocarbon solvents , Octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer that can be used for negative development, if necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,529,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc. can be applied.

  Further, after the step of performing the negative development, a step of stopping the development may be performed while substituting with another solvent.

  After the negative development, it is preferable to include a step of washing with a negative development rinsing solution containing an organic solvent.

  The rinsing liquid used in the rinsing step after negative development is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after the negative development, a cleaning step is performed using a rinsing liquid containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. Even more preferably, after negative development, a step of washing with a rinse solution containing an alcohol solvent or an ester solvent is performed. Particularly preferably, after the negative development, a washing step using a rinsing solution containing a monohydric alcohol is performed. Here, examples of the monohydric alcohol used in the rinsing step after the negative development include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3- Methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3 -Heptanol, 3-octanol, 4-octanol and the like can be used, and 1-hexanol, 2-hexanol, 1-pentanol and 3-methyl-1-butanol are preferable.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing liquid used after negative development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less at 20 ° C. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

In the rinsing step, the wafer that has been subjected to negative development is cleaned using a rinsing solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Synthesis Example 1 (Synthesis of Resin (1))
Under a nitrogen stream, 20 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask and heated to 80 ° C. (solvent 1). The following compound (1a), the following compound (1b), and the following compound (1c) are mixed in a solvent mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a ratio of 40/10/50 to 6/4 (mass ratio). It melt | dissolved and the 22 mass% monomer solution (200g) was prepared. Furthermore, 8 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the monomer, and a dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 1800 ml of hexane / 200 ml of ethyl acetate. The precipitated powder was collected by filtration and dried to obtain 37 g of Resin (1). The obtained resin (1) had a weight average molecular weight of 10,000 and a dispersity (Mw / Mn) of 1.3.

  Resins (2) to (73), (1R), (2R) in the same manner as in Synthesis Example 1 except that monomers corresponding to each repeating unit were used so as to have a desired composition ratio (molar ratio). ) And hydrophobic resins (1a) to (4b) were synthesized. Here, the hydrophobic resins (1a) to (4b) correspond to the resin (D).

  Hereinafter, the structure of resin (2)-(73), (1R), (2R) and resin (1a)-(4b) is shown. Further, including the resin (1) described above, the composition ratio (molar ratio), weight average molecular weight, dispersion of the resins (2) to (73), (1R), (2R) and the resins (1a) to (4b) The degrees are shown in Tables 1 and 2.

Synthesis Example 2 (Synthesis of Compound (PAG-1))
The compound (PAG-1) was synthesized according to [0108] to [0110] of JP2007-161707A.

  Compounds (PAG-2) to (PAG-6) and (PAG-8) to (PAG-9) were also synthesized according to the same method. In addition, CGI * 1907 (made by Ciba Specialty Chemicals) was used for the compound (PAG-7).

  Hereinafter, the structures of the compounds (PAG-1) to (PAG-9) are shown.

<Preparation of resist composition>
The components shown in Tables 3 and 4 below are dissolved in the solvents shown in Tables 3 and 4 to prepare solutions with a solid content concentration of 4% by mass, and each is filtered through a polyethylene filter having a pore size of 0.03 μm. Compositions Ar-1 to Ar-74, Ar-1R and Ar-2R were prepared.

  Abbreviations in Table 3 and Table 4 are as follows.

  B-1 to B-8: each represents the following compound.

W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)

A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: γ-butyrolactone A3: Cyclohexanone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate

  A resist pattern was formed by the following method using the prepared resist composition.

Example 1 (single exposure → negative development: abbreviation EBN)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-01 was applied thereon, and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) and using an exposure mask (line / space = 1/1). After heating at 105 ° C. for 60 seconds, developing with a negative developer for 30 seconds (negative development), rinsing with a rinse solution, and rotating the wafer for 30 seconds at a rotational speed of 4000 rpm, 100 nm (1 1) Line and space resist pattern was obtained.

Examples 2-74 and Comparative Examples 1-2
A line and space resist pattern of 100 nm (1: 1) was obtained in the same manner as in Example 1 except that the resists and conditions described in Tables 5 and 6 were employed.

Example 75 (Single exposure → positive development → negative development: abbreviation EBPN)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-01 was applied thereon, and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through an exposure mask (line / space = 1/1). Thereafter, heating at 105 ° C. for 60 seconds, followed by development with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) (positive developer) for 30 seconds (positive development), rinsing with pure water, a pitch of 480 nm, A pattern with a line width of 360 nm was obtained. Next, after developing for 30 seconds with a negative developer (negative development), rinsing with a rinse solution, and rotating the wafer for 30 seconds at a rotation speed of 4000 rpm, the line and space of 100 nm (1: 1) A resist pattern was obtained.

Comparative Example 3
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 75 except that the resists and conditions shown in Table 6 were used.

Example 76 (Single exposure → negative development → positive development: abbreviation EBNP)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-01 was applied thereon, and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through an exposure mask (line / space = 1/1). After heating at 105 ° C. for 60 seconds, developing with a negative developer for 30 seconds (negative development), rinsing with a rinse solution, and rotating the wafer for 30 seconds at 4000 rpm, the pitch is 400 nm, A pattern with a line width of 300 nm was obtained. Next, the film was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) (positive developer) for 30 seconds (positive development), rinsed with pure water, and 100 nm (1: 1) line and space. A resist pattern was obtained.

Comparative Example 4
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 76 except that the resists and conditions shown in Table 6 were employed.

Example 77 (double exposure → negative development: abbreviation EEBN)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-01 was applied thereon, and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. The obtained wafer was subjected to first pattern exposure using an ArF excimer laser scanner (NA 0.75) via an exposure mask (line / space = 1/1). Next, the mask was rotated in a direction orthogonal to the first exposure, and a second pattern exposure was performed through this. After heating at 105 ° C. for 60 seconds, developing with a negative developer for 30 seconds (negative development), rinsing with a rinse solution, and rotating the wafer for 30 seconds at 4000 rpm, the pitch is 200 nm, A hole pattern with a hole diameter of 100 nm was obtained.

Example 78 (Single exposure → Bake → Positive development → Bake → Negative development: abbreviation EBPBN)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-05 was applied thereon and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. The obtained wafer was subjected to a first pattern exposure using an ArF excimer laser scanner (NA 0.75) through an exposure mask (line / space = 1/1). Thereafter, heating at 95 ° C. for 60 seconds, followed by development with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) (positive developer) for 30 seconds (positive development), rinsing with pure water, a pitch of 400 nm, A pattern with a line width of 300 nm was obtained. Next, after heating at 105 ° C. for 60 seconds, developing with a negative developer for 30 seconds (negative development), rinsing with a rinse solution, and rotating the wafer for 30 seconds at a rotational speed of 4000 rpm, 100 nm A (1: 1) line and space resist pattern was obtained.

Example 79 (single exposure → bake → negative development → bake → positive development: abbreviation EBNBP)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-06 was applied thereon and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. The obtained wafer was subjected to a first pattern exposure using an ArF excimer laser scanner (NA 0.75) through an exposure mask (line / space = 1/1). Thereafter, the film was heated at 95 ° C. for 60 seconds, developed with a negative developer for 30 seconds (negative development), rinsed with pure water, and a pattern having a pitch of 400 nm and a line width of 300 nm was obtained. Next, after heating at 105 ° C. for 60 seconds, developing with a tetramethylammonium hydroxide aqueous solution (2.38 mass%) (positive developer) for 30 seconds (positive development), rinsing with a rinse solution, By rotating the wafer for 30 seconds at a rotational speed of 4000 rpm, a 100 nm (1: 1) line-and-space resist pattern was obtained.

Example 80 (one-time immersion exposure → negative development: abbreviation iE-BN)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-01 was applied thereon and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 150 nm. The obtained wafer was subjected to pattern exposure using an ArF excimer laser immersion scanner (NA 1.20) through an exposure mask (line / space = 1/1). After heating at 105 ° C. for 60 seconds, developing with a negative developer for 30 seconds (negative development), rinsing with a rinsing liquid, and rotating the wafer for 30 seconds at 4000 rpm, the pitch is 110 nm, A pattern with a line width of 55 nm was obtained.

  In Tables 5 and 6, PB means heating before exposure, and PEB means heating after exposure. In the columns of PB, first PEB and second PEB, for example, “115C60s” means heating at 115 ° C. for 60 seconds. A1, A3 and B1 in the negative developer represent the solvents described above. “Negative developer ratio (1) / (2)” and “Rinse solution ratio (1) / (2)” are both weight ratios.

<Evaluation method>
[Line Wid Roughness (LWR)]
A resist pattern of 100 nm (1: 1) line and space (however, in Example 80, 55 nm (1: 1) line and space) was subjected to a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II). ), 50 dotted line widths were measured at equal intervals in the range of 2 μm in the longitudinal direction of the space pattern, and 3σ was calculated from the standard deviation. It shows that it is so that it is so favorable that a value is small (in addition, regarding Example 77, it replaced with evaluation of LWR and evaluated the following HR).

[Hall Roughness (HR)]
The hole pattern obtained in Example 77 was observed by using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and measured by calculating 3σ from the standard deviation of the diameter of the hole pattern. . A smaller value indicates better performance.

[Exposure latitude (EL)]
Exposure for forming a resist pattern having a line and space of 100 nm (1: 1) (however, in Example 77, a hole pattern having a pitch of 200 nm and a hole diameter of 100 nm, and in Example 80, 55 nm (1: 1)). The optimum exposure amount (in the case of multiple development, it means the exposure amount for forming the line and space resist pattern after finally undergoing multiple development, and in the case of multiple development, the line and space resist pattern described above) The first exposure dose for forming the pattern, and when the exposure dose is changed, an exposure dose width that allows a pattern size of 100 nm ± 10% is obtained, and this value is divided by the optimum exposure dose. Displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude (EL).

[Defocus margin (DOF)]
Exposure for forming a resist pattern of 100 nm (1: 1) line and space (however, in Example 77, a hole pattern having a pitch of 200 nm and a hole diameter of 100 nm, and in Example 80, 55 nm (1: 1)). The amount of light and the focus are the optimum exposure amounts (in the case of multiple development, this means the exposure amount for forming the line and space resist pattern after the final multiple development, and in the case of multiple development, the line and space The pattern size is 100 nm ± when the focus is changed (defocused) with the exposure amount set to the optimum exposure amount. The width of the focus allowing 10% was determined. The larger the value, the smaller the performance change due to the focus change, and the better the defocus margin (DOF).

  From Tables 7 and 8, it is clear that the negative developing resist composition of the present invention can stably form a high-precision fine pattern excellent in line width roughness, exposure latitude, and defocus margin. .

It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the conventional method. It is a schematic diagram showing a pattern forming method using both positive development and negative development. It is a schematic diagram which shows the relationship between positive image development, negative image development, and exposure amount. It is the graph which showed the relationship between the exposure amount at the time of using a positive developing solution or a negative developing solution, and a residual film curve. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is a schematic diagram showing the relationship between the positive development, the negative development and the exposure amount in the method of the present invention. It is drawing which shows the spatial intensity distribution of an optical image. It is a schematic diagram which shows the relationship between positive image development, threshold value (a), and light intensity. It is a schematic diagram which shows the spatial intensity distribution of an optical image. It is a schematic diagram which shows the relationship between negative image development, a threshold value (b), and light intensity.

Explanation of symbols

1 Irradiation light 2 Exposure mask 3 Pattern 4 Wafer

Claims (5)

(A) A resin containing a repeating unit having a group having a lactone structure represented by the following general formula (1), wherein the polarity is increased by the action of an acid and the solubility in a negative developer is decreased. A negative resist composition for development.

In general formula (1),
R ₂ independently represents a chain or cyclic alkylene group. When there are a plurality of R _{2 s} , they may be the same or different.
R ₃ each independently represents an alkyl group or a cycloalkyl group. When there are a plurality of R _{3 s,} they may be the same or different, and two R ₃ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom or a sulfur atom.
Y represents an electron withdrawing group each independently. When there are a plurality of Y, they may be the same or different.
Z each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, they may be the same or different.
k is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 1 to 5.
m is the number of substituents and represents an integer of 1 to 7. The repeating unit having a group having a lactone structure represented by the general formula (1) is a repeating unit having a lactone structure represented by the following general formula (2). Negative resist composition for development.

In general formula (2),
R ₁ represents a hydrogen atom, an alkyl group or a halogen atom.
_{R 2, R 3, X,} Y, Z, k, n, m are each, in general formula (1) _{in, R 2, R 3, X} , Y, Z, k, n, in m synonymous is there. (A) forming a film with the negative developing resist composition according to claim 1 or 2,
(A) an exposure process;
(D) a pattern forming method comprising a step of developing using a negative developer.   The negative developer is a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. The pattern forming method according to 1. The resin is a resin whose polarity is increased by the action of an acid to increase the solubility in a positive developer,
5. The pattern forming method according to claim 3, further comprising the step of developing using a positive developer.

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