JP2016133743A - Method for forming resist pattern and method for processing substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a resist pattern, which can improve resist performance, can be applied to an existing coating device without decreasing productivity, and allows formation of a resist pattern with a large film thickness.SOLUTION: The method for forming a resist pattern of the present invention includes a step of forming a resist film from a chemically amplified photoresist composition, a step (1) of heating the resist film, a step (2) of removing heat from the resist film and then heating the resist film, a step of exposing the resist film to light at a wavelength of 248 nm or shorter, and a step of developing the exposed resist film, in which the resist film has a film thickness of 7 μm or more. The method for forming a resist pattern preferably includes, after the above step (2), at least one time of a step (X) of further removing heat from the resist film and then heating the resist film.SELECTED DRAWING: None

Description

  The present invention relates to a resist pattern forming method and a substrate processing method.

  A chemically amplified photoresist composition generates an acid in an exposed area by irradiation with far ultraviolet light typified by KrF excimer laser light or ArF excimer laser light, and the reaction using this acid as a catalyst causes an unexposed area. A resist pattern is formed on the substrate by causing a difference in dissolution rate with respect to the developing solution with the exposed portion (see Japanese Patent Application Laid-Open No. 59-45439).

  A semiconductor device is manufactured by etching a silicon wafer using the resist pattern thus formed as a mask. In recent years, miniaturization of a planar structure of a semiconductor device is reaching a limit, and a memory having a three-dimensional structure has been announced by a semiconductor manufacturer.

  As one method of processing a device into a three-dimensional structure in this way, after etching the substrate using the resist pattern as a mask, the resist pattern is slimmed by a process such as etching to obtain a desired pattern shape, and the substrate is further etched. A method of performing a plurality of etching processes is known. In such a three-dimensional device processing method, the required properties required for a photoresist composition are required to increase the film thickness while maintaining resist performance such as resolution, roughness performance, and etching resistance. It is done.

  However, when the film thickness is increased, the amount of residual solvent in the film increases during normal pre-baking after application of the photoresist composition (hereinafter also referred to as “pre-baking (PAB)”), and heat resistance is caused in the subsequent pattern formation process. This leads to deterioration of the pattern shape due to lack of properties. In addition, since the amount of residual solvent in the film is large, the solvent is volatilized over time during the pattern formation process, so that the pattern dimensions are likely to vary. Therefore, there is a demand for a photoresist composition and a pattern forming method that can suppress shape deterioration and pattern dimension variation due to insufficient heat resistance by appropriately controlling the amount of residual solvent in the resist film.

JP 59-45439 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is not to cause deterioration of the pattern shape due to insufficient heat resistance even at a high film thickness, but to cause variations in pattern dimensions over time during the pattern formation process. It is an object to provide a resist pattern forming method and a substrate processing method capable of suppressing the above.

  The invention made to solve the above problems includes a step of forming a resist film with a chemically amplified photoresist composition, a step (1) of heating the resist film, and a step of heating after removing the heat from the resist film. (2) A resist pattern forming method comprising a step of exposing the resist film at a wavelength of 248 nm or less and a step of developing the exposed resist film, wherein the film thickness of the resist film is 7 μm or more. It is characterized by.

  According to the resist pattern forming method, after the resist film is formed, a normal heating process for reducing the solvent in the resist film is performed after the heating process (1), after removing the heat and heating again (2), By adopting the process, it is possible to form a resist pattern that is free from deterioration of the pattern shape due to heat during the process and variations in pattern dimensions that occur over time even when the film thickness is high. In addition, after the step (2), a resist pattern that is less affected by heat and time during the process is formed by having at least one step (X) of removing the resist film and then heating it. can do.

  The viscosity at 25 ° C. of the chemically amplified photoresist composition is preferably 50 mPa · s or more and 200 mPa · s or less. By setting the viscosity of the chemically amplified photoresist composition in the specific range, in the manufacturing process, the filtration rate and the collection efficiency of foreign matter are not further reduced, and the conventional resist composition application device for excimer laser is applied. In the case of applying to the above, a more necessary flow rate can be secured, and the occurrence of foam biting is further reduced. Moreover, a more uniform coating film can be formed by setting the viscosity of the chemically amplified photoresist composition in the specific range.

The chemically amplified photoresist composition is a polymer having a weight average molecular weight of 1,000 to 15,000 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid (hereinafter referred to as “[A A polymer]), a radiation sensitive acid generator (hereinafter also referred to as “[B] acid generator”) and a solvent (hereinafter also referred to as “[C] solvent”), The solid content of the photoresist composition is preferably 20% by mass or more and 60% by mass or less.
By including a polymer having a weight average molecular weight within the above specified range and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid (hereinafter also referred to as “structural unit (I)”), a chemically amplified type The function as a resist can be exhibited. Further, by using a chemically amplified photoresist composition having a solid content of the above specific range, a resist pattern can be formed using an existing coating apparatus without reducing productivity.

（式（１−１）中、Ｒ^１は、水素原子又は炭素数１〜５のアルキル基である。Ｒ^２は、置換若しくは非置換の炭素数１〜１２のアルキル基、置換若しくは非置換の炭素数１〜１２のアルコキシ基又は置換若しくは非置換の炭素数６〜１２の１価の芳香族炭化水素基である。ａは、１〜３の整数である。ｂは、０〜３の整数である。ａ＋ｂは５以下である。ｂが２以上の場合、複数のＲ^２は同一でも異なっていてもよい。） The polymer preferably further has a structural unit represented by the following formula (1-1) (hereinafter also referred to as “structural unit (II)”). When the polymer has the specific structural unit, the affinity for an alkaline developer can be improved, and as a result, the resist performance of the chemically amplified photoresist composition can be enhanced. The structural unit (II) does not contain an acid dissociable group that is dissociated by the action of an acid.

(In Formula (1-1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted. It is a C1-C12 alkoxy group or a substituted or unsubstituted C1-C12 monovalent aromatic hydrocarbon group, a is an integer of 1-3, b is an integer of 0-3. A + b is not more than 5. When b is 2 or more, a plurality of R ² may be the same or different.

  As a content rate of the said structural unit (II), 20 mol% or more and 90 mol% or less are preferable with respect to all the structural units which comprise a [A] polymer. By making the content rate of the said structural unit (II) into the said specific range, the [A] polymer of an exposure part can fully be dissolved with respect to a developing solution, and the shape of a resist pattern is made favorable. It becomes possible.

  The thickness of the resist film in the resist film forming step is preferably 7 μm or more and 20 μm or less. By setting the thickness of the resist film within the specific range, a resist pattern can be formed more easily and satisfactorily.

  The radiation used in the exposure step is preferably KrF excimer laser light. By using KrF exposure, a resist pattern can be formed more easily and satisfactorily.

  The solvent may include a first solvent (hereinafter also referred to as “[C1] solvent”) having a viscosity at 20 ° C. of 1.5 mPa · s or less. In this case, the content of the [C1] solvent in all the solvents is preferably 60% by mass or more. By including the specific solvent in the specific content, the viscosity of the chemically amplified photoresist composition can be lowered, and the productivity at the time of manufacture and the ease of handling at the time of application can be improved.

  Another invention made in order to solve the above problems is a step of forming a resist film on a substrate with a chemically amplified photoresist composition, a step of heating the resist film (1), and removing heat from the resist film. Then, heating (2), exposing the resist film at a wavelength of 248 nm or less, forming a resist pattern by developing the exposed resist film, and etching the substrate using the resist pattern as a mask And a step of exposing a part of the upper surface of the substrate by etching the resist pattern after the etching step, and after the exposing step, the etching step and the exposing step are repeated at least once in this order. A processing method is characterized in that the resist film has a thickness of 7 μm or more.

  According to the substrate processing method, after the resist film is formed, a normal heating process for reducing the solvent in the resist film is performed after the heating process (1), after removing the heat and heating again (2), By adopting the process, it is possible to form a resist pattern that is free from deterioration of the pattern shape due to heat during the process and variations in pattern dimensions that occur over time even when the film thickness is high. In addition, after the step (2), the substrate is less affected by heat during the etching process by having at least one step (X) of removing the resist film and then heating it after removing the resist film. Can be processed.

  The viscosity at 25 ° C. of the chemically amplified photoresist composition is preferably 50 mPa · s or more and 200 mPa · s or less. By setting the viscosity of the chemically amplified photoresist composition in the specific range, the substrate can be more easily and satisfactorily processed into a three-dimensional structure.

A polymer having a weight average molecular weight of 1,000 to 15,000 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and a radiation-sensitive acid generator It is preferable that the solid content of the chemically amplified photoresist composition is 20% by mass or more and 60% by mass or less.
According to the substrate processing method, since the chemically amplified photoresist composition is used, the substrate can be easily and satisfactorily processed into a three-dimensional structure.

  The polymer preferably further has the structural unit (II). When the polymer has the specific structural unit, the substrate can be processed into a three-dimensional structure more easily and satisfactorily.

  As a content rate of the said structural unit (II), 20 mol% or more and 90 mol% or less are preferable with respect to all the structural units which comprise a [A] polymer. By setting the content ratio of the structural unit (II) within the specific range, the substrate can be further easily and satisfactorily processed into a three-dimensional structure.

  The thickness of the resist film in the resist film forming step is preferably 7 μm or more and 20 μm or less. By setting the thickness of the resist film within the specific range, the substrate can be processed into a three-dimensional structure more easily and satisfactorily.

  The radiation used in the exposure step is preferably KrF excimer laser light. By using KrF exposure, the substrate can be further easily and satisfactorily processed into a three-dimensional structure.

  According to the resist pattern forming method of the present invention, even when the film thickness is high, the pattern shape is not deteriorated due to insufficient heat resistance. A resist pattern with a high film thickness can be formed without reducing the thickness and using an existing coating apparatus. According to the substrate processing method of the present invention, the substrate can be processed into a three-dimensional structure easily and satisfactorily.

<Resist pattern formation method>
The resist pattern forming method includes a step of forming a resist film with a chemically amplified photoresist composition (hereinafter also referred to as “resist film forming step”), a step of heating the resist film (1) (hereinafter referred to as “heating”). Step (1) ”, after removing heat from the resist film, heating (2) (hereinafter also referred to as“ heating step (2) ”), exposing the resist film (hereinafter referred to as“ exposure ”). And a process for developing the exposed resist film (hereinafter also referred to as “development process”), wherein the resist film has a thickness of 7 μm or more. Features. If necessary, after the step (2), the step (X) (hereinafter, also referred to as “heating step (X)”) of removing the resist film and then heating it may be provided at least once.
Hereinafter, the resist pattern forming method will be described.

(Resist film formation process)
In this step, a resist film is formed using a chemically amplified photoresist composition described later. Examples of the substrate on which the resist film is formed include a silicon wafer, a wafer coated with aluminum, and the like. Examples of the coating method include spin coating.

  The film thickness of the resist film is preferably 7 μm or more and 20 μm or less, and more preferably 7 μm or more and 15 μm or less. By setting the film thickness of the resist film within the above specific range, resist performance can be further improved and more sufficient etching resistance can be ensured.

(Heating step (1))
In this step, after applying the chemically amplified photoresist composition, heat treatment is performed at a first temperature of about 70 ° C. to 160 ° C. for 50 to 120 seconds (hereinafter also referred to as “pre-baking (PAB)”).

  In order to prevent the influence of basic impurities contained in the environmental atmosphere, for example, a protective film described in JP-A-5-188598 can be provided on the resist film.

(Heating step (2))
In this step, the resist film heated in the heating step (1) is deheated to a temperature lower than the first temperature and then heated again. The heat removal may be performed until the resist film is usually 20 to 30 ° C., preferably 20 to 25 ° C. Examples of means for removing heat include a cooling plate and standing at room temperature. The heating after heat removal can be the same process as the heating process (1). The heating temperature may be the same as or different from the heating step (1).

(Heating step (X))
This step is a step having at least one step (X) in which the resist film is further removed and heated after the heating step (2), and the number of times can be adjusted appropriately depending on the film thickness and the amount of residual solvent. it can. X represents a natural number of 3 to 10. The conditions for heat removal and the heating conditions in the heating step (X) may be the same as or different from those in the heating step (2). It is preferable that the heating temperature of a heating process (1), a heating process (2), and a heating process (X) is heating process (1) <= heating process (2) <= heating process (X).
It is preferable to perform a heat removal step after the heating step before the exposure step.

[Exposure process]
In this step, the resist film formed in the resist film forming step is exposed at a wavelength of 248 nm or less. This exposure is performed, for example, through a predetermined mask pattern.

  As the electromagnetic wave or charged particle beam used for the exposure, an electromagnetic wave such as ultraviolet ray, far ultraviolet ray, and X-ray, charged particle beam such as electron beam and α ray can be appropriately selected. ArF excimer laser light ( A far ultraviolet ray represented by a wavelength of 193 nm) or KrF excimer laser light (wavelength 248 nm) is preferable, and a KrF excimer laser light (wavelength 248 nm) is particularly preferable. The exposure conditions such as the exposure amount are appropriately selected according to the composition of the chemically amplified photoresist composition, the type of additive, and the like.

  In order to stably form a fine resist pattern with high accuracy, after the exposure, for example, heat treatment at a temperature of 60 ° C. to 160 ° C. for 30 seconds or longer (hereinafter also referred to as “post-exposure bake (PEB)”) Is preferably performed. If the temperature of the PEB is less than 70 ° C., there may be an increase in variation in sensitivity depending on the type of substrate.

[Development process]
In this step, the resist film exposed in the exposure step is developed using an alkaline developer to form a positive resist pattern.

  Alkali developers include alkali metal hydroxides, ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides , Choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, and the like. An alkaline aqueous solution dissolved so as to have a concentration of 10% by mass, preferably 1% by mass to 5% by mass, particularly preferably 1% by mass to 3% by mass is preferably used. In addition, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the alkaline developer.

  The processing conditions in the development step are usually 10 ° C. to 50 ° C. for 10 seconds to 200 seconds, preferably 15 ° C. to 30 ° C. for 15 seconds to 100 seconds, more preferably 20 ° C. to 25 ° C. for 15 seconds to 90 seconds. It is.

For example, an organic solvent can be added to the developer. As such an organic solvent, for example,
Ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone;
Alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol Kind;
Ethers such as tetrahydrofuran and dioxane;
Esters such as ethyl acetate, n-butyl acetate, i-amyl acetate;
Aromatic hydrocarbons such as toluene and xylene;
Phenol, acetonyl acetone, dimethylformamide, etc. are mentioned. In addition, 1 type (s) or 2 or more types can be used for these organic solvents.

  The content ratio of the organic solvent in the developer is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the content ratio of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a concern that the development residue in the exposed part increases. An appropriate amount of a surfactant or the like can be added to the developer. In addition, after developing with a developing solution, it is preferable to wash and dry with water.

<Board processing method>
The substrate processing method includes a step of etching the substrate (hereinafter also referred to as an “etching step”) using the resist pattern formed by the resist pattern forming method as a mask, and etching of the resist pattern after the etching step. A substrate processing method comprising a step of exposing a part of the upper surface of a substrate (hereinafter also referred to as an “exposure step”), and after the exposure step, the etching step and the exposure step are repeated at least once in this order. .

In the etching step, a resist pattern used as an etching mask can be formed by a method similar to the above-described resist pattern forming method.
Hereinafter, the etching process and the exposure process will be described.

[Etching process]
In this step, the substrate is etched using the resist pattern as a mask. This etching is preferably performed under dry etching conditions using a fluorine-based gas. As dry etching conditions, it is preferable to select a gas and a condition in which the etching rate of the substrate is high and the thickness of the upper resist film is small. By this step, the shape of the resist pattern can be transferred to the substrate.

[Exposure process]
In this step, a part of the upper surface of the substrate is exposed by etching the resist pattern after the etching step. The resist pattern may be etched under dry etching conditions using an oxygen-based gas. As dry etching conditions, it is preferable to select a gas and a condition in which the etching rate of the resist film is high and the film loss of the underlying substrate is small. By this step, the resist pattern as a mask used for further etching the substrate can be processed into an arbitrary shape.

  In the substrate processing method, after the exposing step, the etching step and the exposing step are repeated at least once in this order to repeat the substrate surface not covered with the resist film including the newly exposed upper surface of the substrate. Etching can be performed, and the substrate can be processed into a three-dimensional structure.

  If a desired three-dimensional structure is obtained, the remaining resist pattern may be removed by etching after the last etching step.

<Chemically amplified photoresist composition>
Next, a chemically amplified photoresist composition (hereinafter also referred to as “photoresist composition (I)”) that is preferably used in the above-described resist pattern forming method and substrate processing method will be described. The photoresist composition (I) has a weight average molecular weight of 1,000 to 15,000 and a structural unit (I) having an acid dissociable group that is dissociated by the action of an acid [A] polymer, [B] A radiation-sensitive acid generator and a [C] solvent are contained, and the solid content is 20% by mass or more and 60% by mass or less. The photoresist composition (I) may contain a [D] acid diffusion controller, and may contain other components as long as the effects of the present invention are not impaired.

The photoresist composition (I) can be used as, for example, a positive chemically amplified photoresist composition because the polymer [A] has a structural unit (I) containing an acid dissociable group. In the photoresist composition (I), the acid generated from the [B] acid generator or the like dissociates the acid-dissociable group in the exposed area to form a polar group, which is soluble in the developer, and is a positive resist pattern. Can be formed effectively. Here, the “acid-dissociable group” refers to a group that substitutes a hydrogen atom of a polar group such as a hydroxy group or a carboxy group, and dissociates by the action of an acid. Examples of the structural unit (I) containing such an acid-dissociable group include structural units represented by formula (1-2), formula (1-4) and the like described later.
Hereinafter, each component will be described.

<[A] polymer>
[A] The polymer is a polymer having the structural unit (I) containing an acid dissociable group and having a weight average molecular weight of 1,000 or more and 15,000 or less. [A] The polymer preferably has, in addition to the structural unit (I), a structural unit (II) represented by the formula (1-1) described later, a structural unit (III) described later, The structural unit (IV) may be included, and other structural units may be included in addition to the structural units (I) to (IV). [A] The polymer may have one or more of each structural unit.
Hereinafter, each structural unit will be described.

[Structural unit (I)]
The structural unit (I) is a structural unit containing an acid dissociable group. [A] A polymer can form a pattern by having the structural unit (I) containing an acid dissociable group. As the structural unit (I), a structural unit represented by the following formula (1-2) is preferable.

In the above formula (1-2), ^{R 3} is a hydrogen atom or a methyl group. R ⁴ is a monovalent organic group not containing an acid dissociable group. c is an integer of 0-3. When c is 2 or more, the plurality of R ⁴ may be the same or different. R ⁵ is a monovalent acid dissociable group. d is an integer of 1 to 3. When d is 2 or more, the plurality of R ⁵ may be the same or different. However, c + d is 5 or less.

R ³ is preferably a hydrogen atom.

Examples of the monovalent organic group not containing the acid dissociable group represented by R ⁴ include a monovalent hydrocarbon group, a hydroxyalkyl group such as a carboxy group, a hydroxyethyl group, and a hydroxypropyl group, and a hydroxycyclopentyl group. Monovalent nitrogen atoms such as hydroxycycloalkyl groups such as hydroxycyclohexyl groups, alkoxy groups such as methoxy groups and ethoxy groups, cycloalkyloxy groups such as cyclopentyloxy groups and cyclohexyloxy groups, aminoethyl groups and dimethylaminoethyl groups Contains organic groups.

Examples of the monovalent acid dissociable group represented by R ⁵ include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a triorganosilyl group, a triorganogermyl group, an alkoxycarbonyl group, and an acyl group. Group, and a monovalent cyclic acid dissociable group.

  Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, and a methoxyphenacyl group. Group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group , Ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxy Rubonirumechiru group, and the like.

  Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxy. Ethyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl Group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxy Carbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group And the like.

  Examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. .

  Examples of the triorganosilyl group include trimethylsilyl group, ethyldimethylsilyl group, diethylmethylsilyl group, triethylsilyl group, dimethyl i-propylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, Examples thereof include a t-butyldimethylsilyl group, a di-t-butylmethylsilyl group, a tri-t-butylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  Examples of the triorganogermyl group include trimethylgermyl group, ethyldimethylgermyl group, diethylmethylgermyl group, triethylgermyl group, dimethyl i-propylgermyl group, methyldi-i-propylgermyl group, -I-propylgermyl group, t-butyldimethylgermyl group, di-t-butylmethylgermyl group, tri-t-butylgermyl group, dimethylphenylgermyl group, methyldiphenylgermyl group, triphenylgermyl group Etc.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

  Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl Group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isoni Chinoiru group, and the like.

  Examples of the monovalent cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiofuranyl group, Examples thereof include a tetrahydrothiopyranyl group, a 3-bromotetrahydropyranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, and a 3-tetrahydrothiophene-1,1-dioxide group.

  Among these, t-butyl group, benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydro A thiofuranyl group and a tetrahydrothiopyranyl group are preferable, and a t-butyl group is more preferable.

  The c is preferably 0 or 1, and more preferably 0 from the viewpoint of facilitating production. As said d, 1 or 2 is preferable and 1 is more preferable.

  Examples of the polymerizable unsaturated compound giving the structural unit represented by the above formula (1-2) include 4-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4- (2-ethyl- 2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- (1-ethoxyethoxy) -α-methylstyrene, acetoxystyrene, etc. Is mentioned. Of these, 4-t-butoxystyrene is preferred.

  In the case of a positive chemically amplified photoresist composition, the content ratio of the structural unit represented by the above formula (1-2) is 10 mol% with respect to all the structural units constituting the [A] polymer. -45 mol% is preferable and 15 mol%-40 mol% are more preferable. By making the content rate of the structural unit represented by Formula (1-2) into the said specific range, it has favorable sensitivity and can form a high-resolution pattern.

  Another preferred example of the structural unit (I) is a structural unit represented by the following formula (1-4).

In the above formula (1-4), ^{R 8} is a hydrogen atom or a methyl group. R ⁹ is a monovalent acid dissociable group.

R ⁸ is preferably a hydrogen atom.

Examples of the monovalent acid dissociable group represented by R ⁹ include a t-butyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 2-methyladamantyl group, 2-ethyladamantyl group and the like. It is done.

  Examples of the monomer that gives the structural unit represented by the above formula (1-4) include t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, and 1-ethyl (meth) acrylate. Examples include cyclopentyl, 2-methyladamantyl (meth) acrylate, and 2-ethyladamantyl (meth) acrylate.

  In the case of a positive chemically amplified photoresist composition, the content of the structural unit represented by the above formula (1-4) is 0 mol% with respect to all structural units constituting the [A] polymer. -60 mol% is preferable and 10 mol%-50 mol% are more preferable. When the content rate of the structural unit represented by Formula (1-4) exceeds 60 mol%, dry etching resistance may be insufficient.

  Further, the structural unit (I) may be a structural unit represented by the following formula (1-4-a) that forms a crosslinked structure via a divalent acid dissociable group between molecular chains. When the polymer [A] has a structural unit represented by the following formula (1-4-a), the molecular weight of the polymer [A] decreases with the generation of polar groups in the development of the resist film. In the case of a chemically amplified photoresist composition of the type, contrast can be improved.

In the above formula (1-4-a), R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group. R ¹² is a divalent acid dissociable group.

As the ^{R 10} and ^{R 11,} a hydrogen atom is preferable.

Examples of the divalent acid dissociable group represented by R ¹² include 1,1,3,3-tetramethylpropanediyl group, 1,1,4,4-tetramethylbutanediyl group, 1,1 , 5,5-tetramethylpentanediyl group and the like. Among these, 1,1,4,4-tetramethylbutanediyl group is preferable.

  Examples of the monomer that gives the structural unit represented by the above formula (1-4-a) include 2,4-dimethylpentane-2,4-diacrylate, 2,5-dimethylhexane-2,5- Examples include diacrylate and 2,6-dimethylheptane-2,6-diacrylate. Of these, 2,5-dimethylhexane-2,5-diacrylate is preferred.

  As a content rate of the structural unit represented by the said Formula (1-4-a), 10 mol% or less is preferable with respect to all the structural units which comprise a [A] polymer, and 1 mol%-5 mol%. Is more preferable. When the content ratio of the structural unit represented by the formula (1-4-a) exceeds 10 mol%, the pattern forming property of the photoresist composition (I) may be deteriorated.

[Structural unit (II)]
The structural unit (II) is a structural unit represented by the following formula (1-1). [A] By having such a structural unit (II), the polymer can improve the affinity for an alkaline developer.

In the formula (1-1), ^{R 1} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon having 6 to 12 carbon atoms. It is a group. a is an integer of 1 to 3. b is an integer of 0-3. a + b is 5 or less. When b is 2 or more, the plurality of R ² may be the same or different.

R ¹ is preferably a hydrogen atom or a methyl group.

  In the above formula (1-1), the bonding position of the hydroxyl group with respect to the phenyl group is not particularly limited, but when a is 1, the o-position, m-position with respect to the carbon atom bonded to the polymer chain. Either the position or the p-position may be used, and the p-position is preferred. When a is 2 or 3, the bonding position is arbitrary.

The alkyl group having 1 to 12 carbon atoms represented by R ² may be linear or branched, such as a methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned.

The alkoxy group having 1 to 12 carbon atoms represented by R ² may be linear or branched, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, Examples include n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and the like.

Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ² include a phenyl group, a benzyl group, and a tolyl group.

Examples of the substituent that the alkyl group, alkoxy group and aryl group of R ² may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group, carboxy group, nitro group and cyano group Etc. The group may have one or more of the above substituents alone, or may have one or more of each of the plurality.

R ² is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.

  As said a, 1 or 2 is preferable and 1 is more preferable. The b is preferably 0 or 1, and more preferably 0 from the viewpoint of facilitating production. Particularly preferred as the structural unit represented by the above formula (1-1) is a structural unit formed by cleavage of a polymerizable unsaturated bond of 4-hydroxystyrene.

  As a content rate of the said structural unit (II), 20 mol%-90 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 30 mol%-85 mol% are more preferable, 40 mol% % To 80 mol% is more preferable. By setting it as such a content rate, the [A] polymer of an exposure part can fully be dissolved with respect to a developing solution, and it becomes possible to make the shape of a resist pattern favorable.

[Structural unit (III)]
The structural unit (III) is a structural unit represented by the following formula (1-3).

In the above formula (1-3), ^{R 6} is a hydrogen atom or a methyl group. R ⁷ is a monovalent hydrocarbon group or a non-acid-dissociable monovalent oxyhydrocarbon group. e is an integer of 0-3. When e is 2 or more, the plurality of R ⁷ may be the same or different.

R ⁶ is preferably a hydrogen atom.

Examples of the monovalent hydrocarbon group represented by R ⁷ include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group; a cyclopentyl group, a cyclohexyl group, and the like. A cycloalkyl group; an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, and a benzyl group;

Examples of the non-acid dissociable monovalent oxyhydrocarbon group represented by R ⁷ include primary or 2 such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group and the like. Grade alkoxy groups; cycloalkyloxy groups such as cyclopentyloxy groups and cyclohexyloxy groups; and oxyaromatic hydrocarbon groups such as phenoxy groups and benzyloxy groups.

Among these, R ⁷ is preferably an alkyl group or an alkoxy group, more preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group, still more preferably a methyl group or a methoxy group, and particularly preferably a methyl group.

  As said e, the integer of 0-2 is preferable, 0 or 1 is more preferable, and 0 is further more preferable.

  Examples of the monomer that gives the structural unit (III) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4- And methoxystyrene. Of these, styrene is preferred.

  In the case of a positive chemically amplified photoresist composition, the content of the structural unit (III) is preferably 20 mol% or less, and 0 mol with respect to all structural units constituting the [A] polymer. % To 10 mol% is more preferable. If the content ratio of the structural unit (III) exceeds 20 mol%, the developability of the resist film may be lowered.

[Other structural units]
[A] The polymer may have other structural units in addition to the structural units (I) to (III).
Examples of the other structural units include:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate 1-methylpropyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxy-n-propyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 1-methyl-2-adamantyl, 1-ethyl-2-adamantyl (meth) acrylate, (meth) acrylic acid 8- Tyl-8-tricyclodecyl, 8-ethyl-8-tricyclodecyl (meth) acrylate, 3-methyl-3-tetracyclododecenyl (meth) acrylate, 3-ethyl (meth) acrylate (Meth) acrylic acid esters such as 3-tetracyclododecenyl and 2,5-dimethylhexane-2,5-di (meth) acrylate;
Unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxy-n-propyl (meth) acrylate, 3-carboxy-n-propyl (meth) acrylate;
Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile;
Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide;
Unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole And structural units (IV) derived from monomers of nitrogen-containing vinyl compounds such as 4-vinylimidazole. The structural unit (IV) does not contain an acid dissociable group.

  As a content rate of the said structural unit (IV), it is 25 mol% or less normally with respect to all the structural units which comprise a [A] polymer, and 15 mol% or less is preferable. When the content ratio of the structural unit (IV) exceeds 25 mol%, the resolution of the resist pattern to be formed may be lowered.

  The [A] polymer preferably has a structural unit containing an aromatic ring. As a content rate of the structural unit containing this aromatic ring, 50 mol% or more and 100 mol% or less are preferable, 70 mol% or more and 100 mol% or less are more preferable, and 80 mol% or more and 100 mol% or less are more preferable. [A] Since the polymer has the structural unit in the specific range, sufficient etching resistance can be ensured even in a process having a plurality of etching steps such as three-dimensional device processing.

  [A] Examples of the polymer include, for example, 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / acrylic acid 1-methylcyclopentyl copolymer, 4 -Hydroxystyrene / 4-t-butoxystyrene / acrylic acid 1-ethylcyclopentyl copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / styrene copolymer, 4-hydroxystyrene / t-butyl acrylate / styrene Copolymer, 4-hydroxystyrene / 1-methylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 1-ethylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 2,5-dimethylhexane-2,5-diacrylate Polymer, 4-hydroxystyrene / 2-ethyladamantyl acrylate / styrene copolymer, 4-hydroxystyrene / 2-ethyladamantyl acrylate copolymer, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene / 4-tert-butoxystyrene copolymer, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene copolymer, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene / styrene copolymer, 4- Examples thereof include hydroxystyrene / 4-t-butoxystyrene / N, N-dimethylacrylamide copolymer. Among these, 4-hydroxystyrene / 4-t-butoxystyrene / styrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 2,5-dimethylhexane-2,5-diacrylate copolymer And 4-hydroxystyrene / 4-t-butoxystyrene / N, N-dimethylacrylamide copolymer is preferred.

<[A] Polymer Synthesis Method>
[A] The method for synthesizing the polymer is not particularly limited, and a conventionally known method can be used. For example, (i) a monomer in which the phenolic hydroxyl group of substituted or unsubstituted hydroxystyrene is protected with a protecting group, such as butoxycarbonyloxystyrene, butoxystyrene, acetoxystyrene, tetrahydropyranyloxystyrene, and the structural unit ( (Ii) a method in which a protective group is hydrolyzed and eliminated by addition polymerization of a monomer that gives a predetermined structural unit other than II) and then reacting with an acid catalyst or a base catalyst; Examples thereof include a method of subjecting unsubstituted hydroxystyrene to addition polymerization together with a monomer corresponding to a predetermined structural unit other than the structural unit (II). Among these, the method (i) is preferable from the viewpoint of efficiently synthesizing the [A] polymer.

  Examples of the addition polymerization include radical polymerization, anionic polymerization, cationic polymerization, and thermal polymerization. Anionic polymerization and cationic polymerization can reduce the degree of dispersion (Mw / Mn ratio) of the resulting copolymer. Is preferable.

  Examples of the acid catalyst used for the hydrolysis reaction in the method (i) include inorganic acids such as hydrochloric acid and sulfuric acid. Examples of the base catalyst include organic bases such as trialkylamine and inorganic bases such as sodium hydroxide.

  [A] The lower limit of the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is 1,000, preferably 2,000, and more preferably 3,000. The upper limit of Mw is 15,000, preferably 12,000, more preferably 7,500, still more preferably 7,000, and particularly preferably 6,500.

  [A] The ratio (Mw / Mn) between the polymer Mw and the polystyrene-equivalent number average molecular weight (Mn) by GPC is preferably 1 to 3, and more preferably 1 to 2.

  The above Mw and Mn were measured using Tosoh's GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL), flow rate 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. The value measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

  The content of the [A] polymer in the photoresist composition (I) is usually 70% by mass or more and 80% by mass with respect to the total solid content (total mass of components other than the [C] solvent). The above is preferable, and 90% by mass or more is more preferable. [A] A polymer can use 1 type (s) or 2 or more types.

<[B] Acid generator>
[B] The acid generator is a component that generates an acid upon exposure. The acid-dissociable group of the [A] polymer or the like is dissociated by the generated acid to generate an acidic group or the like, and the resist pattern is formed by changing the solubility of the [A] polymer in the developer. Can do. The content of the [B] acid generator in the photoresist composition (I) may be a low molecular compound form (hereinafter also referred to as “[B] acid generator” as appropriate), as described later. It may be a form incorporated as a part or both of these forms. [B] The acid generator may contain 1 type (s) or 2 or more types.

  [B] The acid generator is preferably a nonionic acid generator. Examples of the nonionic acid generator include N-sulfonyloxyimide compounds represented by the following formula (B1).

In the above formula (B1), R ¹⁵ is an alkylene group, an arylene group, an alkoxylene group, a cycloalkylene group, or a divalent group including a cyclic skeleton having an unsaturated bond. R ¹⁶ represents an alkyl group which may be substituted with a halogen atom or a cycloalkyl group, a cycloalkyl group which may be substituted with a group having an ester bond, an aryl group which may be substituted with a halogen atom or an alkyl group Or an aralkyl group which may be substituted with a fluorine atom, a hydroxy group, an alkoxy group or a carboxy group.

  Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide. N- (4-toluenesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-{(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) Sulfonyloxy} succinimide and the like.

  As the nonionic acid generator, a sulfonyldiazomethane compound is also preferable. Examples of the sulfonyldiazomethane compound include a compound represented by the following formula (B2).

In the formula (B2), R ¹⁷ and R ¹⁸ are each independently an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom, or a halogen atom. An aryl group which may be substituted, or an aralkyl group which may be substituted with a fluorine atom, a hydroxy group, an alkoxy group or a carboxy group.

  Examples of the sulfonyldiazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). Diazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorobenzenesulfonyl) diazomethane, methylsulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 1,1-dimethylethane Sulfonyldiazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane, bis (1-methylethanesulfonyl) Azomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane, etc. It is done.

  [B] An onium salt can also be used as the acid generator.

  Examples of the onium salt compound include compounds represented by the following formula (B3) or (B4).

In the above formula (B3), R ¹⁹ and R ²⁰ each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 6 carbon atoms. 18 represents an aryl group or a cyclic structure in which these groups are combined with each other and combined with an iodine atom to which they are bonded.
In the above formula (B4), R ²¹ , R ²² and R ²³ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon. An aryl group of 6 to 18 or a cyclic structure in which two of these groups are combined with each other and together with the sulfur atom to which they are bonded, and the remaining one is a substituted or unsubstituted carbon number 1 to 10 linear or branched alkyl group or substituted or unsubstituted aryl group having 6 to 18 carbon atoms.
In the above formulas (B3) and (B4), X ⁻ is R—SO ₃ ^— . R is unsubstituted or an alkyl group which may be substituted with a fluorine atom, a hydroxy group, an alkoxy group or a carboxy group, a cycloalkyl group which may be substituted with a fluorine atom, a hydroxy group, an alkoxy group or a carboxy group, fluorine An aryl group which may be substituted with an atom, a hydroxy group, an alkoxy group or a carboxy group, or an aralkyl group which may be substituted with a fluorine atom, a hydroxy group, an alkoxy group or a carboxy group.

The R-SO ₃ ^- as is trifluoromethanesulfonate, nonafluoro -n- butane sulfonate, benzene sulfonate, 10-camphorsulfonate, 2-trifluoromethylbenzene sulfonate, 4-trifluoromethyl benzene sulfonate, 2,4-difluorobenzene Sulfonate, perfluorobenzene sulfonate, 2- (bicyclo [2.2.1] heptan-2-yl) -1,1-difluoroethane sulfonate, 2- (bicyclo [2.2.1] heptan-2-yl) ethane Sulfonate is preferred.

  Examples of the [B] acid generator other than the above include disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.

  Examples of the disulfonylmethane compound include compounds represented by the following formula (B5).

In the above formula (B5), R ²⁴ and R ²⁵ are each independently a monovalent hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent group having a hetero atom. Organic group. V and W are each independently a hydrogen atom, an aryl group, a linear or branched monovalent hydrocarbon group, a monovalent organic group having a hetero atom, and at least one of V and W is an aryl group. Or a carbon monocyclic structure having at least one unsaturated bond constituted by V and W being combined with each other, or a carbon polycyclic structure having at least one unsaturated bond, or V and W may be combined with each other to form a group represented by the following formula (B6).

  In the formula (B6), V ′ and W ′ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, or the same. V ′ and W ′ bonded to each other or different carbon atoms are combined with each other to form a carbon monocyclic structure. n is an integer of 2 to 10. When n is 2 or more, the plurality of V ′ may be the same or different, and the plurality of W ′ may be the same or different.

  Examples of the oxime sulfonate compound include compounds represented by the following formula (B7) or (B8).

In the above formula (B7), R ²⁶ and R ²⁷ are each independently a monovalent organic group.
In the formula (B8), R ^{28 to} R ³¹ are each independently a monovalent organic group.

  [B] The content of the acid generator is, when the [B] acid generator is a [B] acid generator, 0.1 to 30 parts by mass with respect to 100 parts by mass of the [A] polymer. Preferably, 0.5 mass part-20 mass parts is more preferable. [B] When the content of the acid generator is 0.1 parts by mass or more, the sensitivity and developability of the photoresist composition (I) become appropriate. On the other hand, when the content of the [B] acid generator is 30 parts by mass or less, transparency, pattern shape, heat resistance and the like of the formed resist film with respect to radiation are improved.

<[C] solvent>
[C] The solvent is not particularly limited as long as it can dissolve at least the [A] polymer, the [B] acid generator, and other components added as necessary. [C] The solvent may contain 1 type (s) or 2 or more types.

  The [C] solvent preferably includes a [C1] solvent having a viscosity at 20 ° C. of 1.5 mPa · s or less. [C1] The lower limit of the viscosity of the solvent is preferably 0.1 mPa · s. Moreover, as content in the [C] solvent of a [C1] solvent, 60 mass% or more and 100 mass% or less are preferable, and 65 mass% or more and 100 mass% or less are more preferable. By using such a [C1] solvent, the viscosity of the photoresist composition (I) can be lowered, and the productivity during production and the ease of handling during coating can be improved.

  The [C1] solvent preferably contains at least one selected from the group consisting of ester compounds and chain ketone compounds.

Examples of the ester compound include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Alkylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate;
Methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, ethyl propionate, n-butyl propionate, i-propionate Aliphatic carboxylic acid esters such as amyl;
Examples include other esters such as ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and methyl acetoacetate.
Among these,
As the alkylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is more preferable.
As the aliphatic carboxylic acid ester, acetate ester is preferable, and n-butyl acetate is more preferable.
Other esters are preferably methoxypropionic acid esters, and more preferably methyl methoxypropionate.

  Examples of the chain ketone compound include methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, and 4-heptanone. Of these, 2-heptanone is preferred.

  [C1] The solvent preferably contains at least one selected from the group consisting of alkylene glycol monoalkyl ether acetates, aliphatic carboxylic acid esters, and chain ketone compounds, and more preferably includes two selected from the above group. preferable. [C1] When the solvent contains the above compound, the viscosity of the photoresist composition (I) can be made more appropriate.

  The [C] solvent preferably further includes a [C2] solvent that is at least one selected from the group consisting of a compound having a hydroxy group and a cyclic ketone compound.

  Examples of the compound having a hydroxy group include ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether. And propylene glycol monoalkyl ether. Of these, ethyl lactate is preferred.

  Examples of the cyclic ketone compound include cyclohexanone, cyclopentanone, dihydrofuran-2 (3H) -one, and the like. Of these, cyclohexanone is preferred.

  The above-mentioned [C] solvent may contain other solvents other than the above-mentioned [C1] solvent and [C2] solvent for the purpose of dissolving the solid content and adjusting the viscosity.

As said other solvent, for example,
Aromatic hydrocarbons such as toluene and xylene;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-n-butyl ether;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolacun.

<[D] Acid diffusion controller>
The photoresist composition (I) preferably contains a [D] acid diffusion controller. [D] The acid diffusion control body controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator or the like by exposure, and has an action of suppressing an undesirable chemical reaction in the non-exposed region. The inclusion form of the [D] acid diffusion controller in the photoresist composition (I) may be a low molecular compound form (hereinafter also referred to as “[D] acid diffusion controller” as appropriate) or a polymer. May be incorporated as a part of or both of these forms. [D] The acid diffusion controller may contain one or more kinds.

  [D] Examples of the acid diffusion controller include nitrogen-containing organic compounds and photosensitive basic compounds. Examples of the nitrogen-containing organic compound include a compound represented by the following formula (D-1) (hereinafter also referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (i)”). , Also referred to as “nitrogen-containing compound (ii)”), polymers of polyamino compounds and nitrogen-containing polymerizable compounds having 3 or more nitrogen atoms (hereinafter, these are collectively referred to as “nitrogen-containing compound (iii)”), Examples include amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

In said formula (D-1), R ^<32> , R ^<33> and R ^<34> are respectively independently a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted.

  Examples of the nitrogen-containing compound (i) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, etc. Of the aromatic amines.

  Examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenylether. 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2, -(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) ) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl ester Benzene], bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′ , N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like.

  Examples of the nitrogen-containing compound (iii) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt- Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-( -)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1 , 7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di- t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric acid tris (2-hydroxyethyl) and the like.

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine , Nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, pyridines such as 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxyethyl ) In addition to piperazines such as piperazine, pyra , Pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. Among these, imidazoles are preferable. -Phenylbenzimidazole is more preferred.

  The photosensitive basic compound is a component having a property of efficiently decomposing into a corresponding neutral substance in an exposed region and remaining as it is without decomposing in an unexposed portion. Such a photosensitive basic compound can improve the sensitivity because it can effectively use the acid generated in the exposed area as compared with the non-photosensitive basic compound.

  Although it does not specifically limit as said photosensitive basic compound as long as it has the said property, The compound represented by a following formula (D2-1) or (D2-2) is used suitably.

In the above formulas (D2-1) and (D2-2), R ^{35 to} R ³⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a monovalent group having 3 to 10 carbon atoms. Are alicyclic hydrocarbon groups or alkoxy groups having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group, and alkoxy group may be substituted. E ^- and Q ^- are each ^{independently,} OH ^-, R D -O - or ^R D -COO ^- a. However, ^RD is a monovalent organic group.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

As a C1-C10 alkyl group represented by said R < ³⁵ > -R < ³⁹ >, a methyl group, an ethyl group, n-butyl group, t-butyl group etc. are mentioned, for example.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ^{35 to} R ³⁹ include, for example, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, a norbornyl group, a norbornenyl group, And an adamantyl group.

  Examples of the substituent for the alkyl group and alicyclic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an alkoxy group.

As a C1-C10 alkoxy group represented by said R < ³⁵ > -R < ³⁹ >, a methoxy group, t-butoxy group, etc. are mentioned, for example.

  Examples of the substituted alkyl group, alicyclic hydrocarbon group, and alkoxy group include a trifluoromethyl group, a trichloromethyl group, a perfluorocyclopentyl group, and a t-butoxycarbonylmethyloxy group.

As said R < ³⁵ > -R < ³⁹ >, a hydrogen atom and a t-butyl group are preferable and a hydrogen atom is more preferable.

Examples of the monovalent organic group represented by ^RD include an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. Good aryl groups and the like can be mentioned.

The anion represented by E ⁻ and Q ⁻ is at least one selected from the group consisting of OH ⁻ , CH ₃ COO ⁻ , and anions represented by the following formulas (X-1) to (X-8). Is preferred.

The photosensitive basic compound is a triphenylsulfonium compound (compound represented by the above formula (D2-1)), and its anion (E ⁻ ) is OH ⁻ , CH ₃ COO ⁻ , and the above formula. The compound which is at least 1 sort (s) chosen from the anion represented by (X-5) and Formula (X-7) is preferable.

  [D] The content of the acid diffusion controller is preferably 15 parts by mass or less with respect to 100 parts by mass of the polymer [A] when the [D] acid diffusion controller is a [D] acid diffusion controller. 0.001 to 10 parts by mass is more preferable, 0.005 to 5 parts by mass is further preferable, and 0.05 to 3 parts by mass is particularly preferable. [D] When the content of the acid diffusion controller exceeds 15 parts by mass, the sensitivity as a resist and the developability of the exposed part may be lowered. On the contrary, if the content is less than 0.001 part by mass, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

<Other ingredients>
The photoresist composition (I) is a surfactant, a sensitizer, a dye, a pigment, an adhesion aid, an antihalation agent such as 4-hydroxy-4′-methylchalcone, and other shapes as necessary as other optional components. It may contain an improving agent, a storage stabilizer, an antifoaming agent and the like.

<Method for Preparing Chemically Amplified Photoresist Composition>
The photoresist composition (I) is prepared, for example, by mixing a [A] polymer, a [B] acid generator, other components contained as necessary, and a [C] solvent in a predetermined ratio, and then filtering with a filter. To be prepared.

  The lower limit of the solid content of the photoresist composition (I) is 20% by mass, preferably 25% by mass. As an upper limit of solid content, it is 60 mass%, and 55 mass% is preferable.

  The pore size of the filter used for filtration is usually 1.0 μm or less and preferably 0.5 μm or less. Even if the photoresist composition (I) has a high solid content, the viscosity is low, so that even a filter having a small pore size can be filtered without reducing the production efficiency.

  The lower limit of the viscosity of the photoresist composition (I) at 25 ° C. is preferably 50 mPa · s, more preferably 60 mPa · s. The upper limit of the viscosity is 200 mPa · s, preferably 170 mPa · s, more preferably 150 mPa · s, further preferably 130 mPa · s, particularly preferably 110 mPa · s, and still more preferably 90 mPa · s. By making the viscosity within the above specific range, it is more necessary in the production process without lowering the filtration rate and foreign matter collection efficiency, and when applied to a conventional excimer laser resist composition coating apparatus. The flow rate can be secured and the occurrence of bubble biting is further reduced. As a result, a uniform film can be formed even with a high film thickness of 7 μm or more.

  The photoresist composition (I) is preferably for KrF exposure. The photoresist composition (I) can be particularly suitably used in KrF exposure from the viewpoint of pattern size and etching resistance.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of various physical property values is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Mw and Mn of the polymer were analyzed using Tosoh GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) at a flow rate of 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

[ ¹³ C-NMR analysis]
The ¹³ C-NMR analysis of the polymer was measured using a nuclear magnetic resonance apparatus (“JNM-ECX400” manufactured by JEOL Ltd.).

<[A] Synthesis of polymer>
[Synthesis Example 1]
910 g of a compound represented by the following formula (L-1), 358 g of a compound represented by the following formula (L-2), 37 g of a compound represented by the following formula (L-3), azobisisobutyronitrile (AIBN) ) 105 g and 55 g of t-dodecyl mercaptan were dissolved in 160 g of propylene glycol monomethyl ether, followed by polymerization for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane, and the produced polymer was coagulated and purified. Next, after adding 1,500 g of propylene glycol monomethyl ether again to the polymer obtained by purification, 3,000 g of methanol, 800 g of triethylamine and 150 g of water are further added, and water is added for 8 hours while refluxing at the boiling point. A decomposition reaction was performed. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting polymer was dissolved in acetone, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and filtered at 50 ° C. under reduced pressure overnight. It dried and the polymer (A-1) was obtained. The obtained polymer (A-1) had Mw of 4,500 and Mw / Mn of 1.8. Moreover, as a result of ¹³ C-NMR analysis, each structural unit represented by the following formula (A-1) was included, and the content ratio (mol%) of each structural unit was a / b / c = 70.1 / It was 25.4 / 4.5.

[Synthesis Example 2]
940 g of the compound represented by the above formula (L-1), 325 g of the compound represented by the above formula (L-2), 40 g of the compound represented by the above formula (L-3), azobisisobutyronitrile (AIBN) ) 79 g and 10 g of t-dodecyl mercaptan were dissolved in 1,600 g of propylene glycol monomethyl ether, followed by polymerization for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane, and the produced polymer was coagulated and purified. Next, after adding 1,500 g of propylene glycol monomethyl ether again to the polymer obtained by purification, 3,000 g of methanol, 800 g of triethylamine and 150 g of water are added, and water is added for 8 hours while refluxing at the boiling point. A decomposition reaction was performed. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting polymer was dissolved in acetone, then dropped into a large amount of water to solidify, and the resulting white powder was filtered and filtered at 50 ° C. under reduced pressure overnight. It dried and the polymer (A-2) was obtained. The obtained polymer (A-2) had Mw of 12,000 and Mw / Mn of 1.7. Moreover, it has each structural unit represented by the said Formula (A-1) as a result of < ¹³ > C-NMR analysis, The content rate (mol%) of each structural unit is a / b / c = 72.2. /23.1/4.7.

<Preparation of chemically amplified photoresist composition>
Each component other than the [A] polymer used for the preparation of the chemically amplified photoresist composition is shown below.

[[B] acid generator]
B-1: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide

[[C] solvent]
([C1] solvent)
C1-1: Propylene glycol monomethyl ether acetate (viscosity at 20 ° C .: 1.3 mPa · s)
C1-2: n-butyl acetate (viscosity at 20 ° C .: 0.74 mPa · s)

[[D] acid diffusion controller]
D-1: 2-Phenylbenzimidazole

[Preparation Example 1]
[A] 100 parts by mass of (A-1) as a polymer, [B] 6 parts by mass of (B-1) as an acid generator, and [C1] a solvent as a [C] solvent (C1-1) 178 parts by mass and [D] 0.4 part by mass of (D-1) acid diffusion controller were mixed to form a uniform solution, and then filtered through a pore size of 1.0 μm, to obtain a chemically amplified photoresist composition (J-1) was prepared.

[Preparation Examples 2 and 3]
Chemically amplified photoresist compositions (J-2) and (J-3) were prepared in the same manner as Preparation Example 1 except that the components having the types and contents shown in Table 1 below were used.

<Formation of resist film>
[Examples 1-6 and Comparative Examples 1-5]
Each chemically amplified photoresist composition prepared above was spin-coated on a silicon wafer and then pre-baked (PAB) and heat removal shown in Table 2 to form a resist film having a thickness of 8 μm.
Each PAB and heat removal step in Table 2 indicates that heat removal 1 was performed after PAB1, and those with PAB2 were subjected to PAB2 after heat removal 1, and heat removal 2 was performed after PAB2. Represents that. The same applies to PAB3 and heat removal 3.

<Evaluation>
The prepared photoresist composition and the formed resist film were evaluated according to the following methods. Table 1 shows the measurement results of the viscosity of the chemically amplified photoresist composition, and Table 2 shows the evaluation results of heat resistance and PCD.

[Resist film thickness]
It measured using the optical interference type film thickness measuring apparatus ("VM-2010" of Dainippon Screen Manufacturing Co., Ltd.) (The unit of film thickness is micrometer).

[viscosity]
The same composition as the chemically amplified photoresist composition used in the resist film thickness measurement was measured using an E-type viscometer (“RE-80L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 4 rpm ( The unit of viscosity is mPa · s).

[Heat-resistant]
Each resist film obtained was exposed to KrF excimer laser (wavelength 248 nm) through a mask pattern using a KrF excimer laser irradiation apparatus (Nisson's “NSR-S203B”), and then subjected to PEB at 110 ° C. for 90 seconds. A 50 μm trench pattern was formed. Thereafter, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used as a developing solution, developed at 23 ° C. for 60 seconds, washed with water for 30 seconds, and dried to form a resist pattern. The obtained resist pattern was heated at 130 ° C. for 5 minutes and observed using a scanning electron microscope (“S-4800” manufactured by Hitachi High-Technologies Corporation). The heat resistance was evaluated as “◯” when no heat deformation was observed at 130 ° C., and “X” when heat deformation was observed at 130 ° C.

[PCD]
In each Example, when the resist film subjected to PAB (X) and heat removal (X) shown in Table 2 was patterned as it was, and after performing PAB (X) and heat removal (X) shown in Table 2 Compare the pattern size when the pattern is formed after placement in an environment in a clean room for 24 hours. If the absolute value of the amount of change (PCD) is 50 nm or less, “○”, and if it exceeds 50 nm, “×”. evaluated.
The above pattern uses a KrF excimer laser irradiation device (Nikon's "NSR-S203B") for each PAB, heat removal and holding conditions, and masks the KrF excimer laser (wavelength 248 nm). After exposure through the pattern, PEB was performed at 110 ° C. for 90 seconds to form a 3 μm trench pattern. Thereafter, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used as a developing solution, developed at 23 ° C. for 60 seconds, washed with water for 30 seconds, and dried to form a resist pattern. The obtained resist pattern was observed using a CD-scanning electron microscope (“S-9220” manufactured by Hitachi High-Technologies Corporation).

  As can be seen from the results in Table 2, according to the resist pattern forming method of the embodiment, even when the film thickness is high, the pattern shape is not deteriorated due to insufficient heat resistance, and the variation of the pattern dimension occurring over time during the pattern forming process is suppressed. can do. Only by extending the PAB time without removing heat (Comparative Examples 2 to 4) or by increasing the PAB temperature (Comparative Example 5), there is no sufficient heat resistance, and pattern deformation is seen, and also due to aging during the process It was found that the dimensional variation was large.

  According to the resist pattern forming method of the present invention, the resist performance can be improved, and it is difficult to be influenced by the aging during the process. Therefore, the productivity is not lowered, and a high film is formed using an existing coating apparatus. A thick resist pattern can be formed. According to the substrate processing method of the present invention, the substrate can be processed into a three-dimensional structure easily and satisfactorily.

Claims (26)

Forming a resist film with a chemically amplified photoresist composition;
Heating the resist film (1),
Step (2) of heating after removing heat from the resist film,
A resist pattern forming method comprising: exposing the resist film at a wavelength of 248 nm or less; and developing the exposed resist film,
A resist pattern forming method, wherein the resist film has a thickness of 7 μm or more. After the step (2),
Furthermore, the resist pattern formation method of Claim 1 which has the process (X) heated after removing the said resist film at least once.   The resist pattern forming method according to claim 1, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C. of 50 mPa · s to 200 mPa · s.   The method for forming a resist pattern according to claim 1 or 2, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C of 50 mPa · s to 170 mPa · s.   The method for forming a resist pattern according to claim 1 or 2, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C of 50 mPa · s to 150 mPa · s. A polymer having a weight average molecular weight of 1,000 to 15,000 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and a radiation-sensitive acid generator Body and solvent,
The resist pattern forming method according to claim 1, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. A polymer having a weight average molecular weight of 1,000 or more and 12,000 or less and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and generation of a radiation-sensitive acid Body and solvent,
The resist pattern forming method according to claim 1, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. A polymer having a weight average molecular weight of 1,000 to 7,500 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and a radiation-sensitive acid generator Body and solvent,
The resist pattern forming method according to claim 1, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. The resist pattern forming method according to claim 6, wherein the polymer further has a structural unit represented by the following formula (1-1).

(In Formula (1-1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted. It is a C1-C12 alkoxy group or a substituted or unsubstituted C1-C12 monovalent aromatic hydrocarbon group, a is an integer of 1-3, b is an integer of 0-3. A + b is not more than 5. When b is 2 or more, a plurality of R ² may be the same or different.   The resist pattern formation according to claim 9, wherein a content ratio of the structural unit represented by the formula (1-1) is 20 mol% or more and 90 mol% or less with respect to all the structural units constituting the polymer. Method.   The resist pattern forming method according to any one of claims 1 to 10, wherein a film thickness of the resist film in the resist film forming step is not less than 7 µm and not more than 20 µm.   The method for forming a resist pattern according to any one of claims 1 to 11, wherein the radiation used in the exposure step is KrF excimer laser light. The solvent includes a first solvent having a viscosity at 20 ° C. of 1.5 mPa · s or less,
13. The resist pattern forming method according to claim 6, wherein the content of the first solvent in all the solvents is 60% by mass or more. Forming a resist film on a substrate with a chemically amplified photoresist composition;
Heating the resist film (1),
Step (2) of heating after removing heat from the resist film,
Exposing the resist film at a wavelength of 248 nm or less;
Forming a resist pattern by developing the exposed resist film;
Using the resist pattern as a mask, etching the substrate, and exposing the upper surface of the substrate by etching the resist pattern after the etching step,
A substrate processing method in which the etching step and the exposure step are repeated at least once in this order after the exposure step,
A method of processing a substrate, wherein the resist film has a thickness of 7 μm or more. After the step (2),
Furthermore, the processing method of the board | substrate of Claim 14 which has the process (X) heated after removing the said resist film at least once.   The method for processing a substrate according to claim 14 or 15, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C of from 50 mPa · s to 200 mPa · s.   The method for processing a substrate according to claim 14 or 15, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C of from 50 mPa · s to 170 mPa · s.   The method for processing a substrate according to claim 14 or 15, wherein the chemically amplified photoresist composition has a viscosity at 25 ° C of from 50 mPa · s to 150 mPa · s. A polymer having a weight average molecular weight of 1,000 to 15,000 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and a radiation-sensitive acid generator Body and solvent,
19. The substrate processing method according to claim 14, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. A polymer having a weight average molecular weight of 1,000 or more and 12,000 or less and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and generation of a radiation-sensitive acid Body and solvent,
19. The substrate processing method according to claim 14, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. A polymer having a weight average molecular weight of 1,000 to 7,500 and having a structural unit containing an acid dissociable group that is dissociated by the action of an acid, and a radiation-sensitive acid generator Body and solvent,
19. The substrate processing method according to claim 14, wherein the chemically amplified photoresist composition has a solid content of 20% by mass or more and 60% by mass or less. The substrate processing method according to claim 19, 20 or 21, wherein the polymer further has a structural unit represented by the following formula (1-1).

(In Formula (1-1), R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted. It is a C1-C12 alkoxy group or a substituted or unsubstituted C1-C12 monovalent aromatic hydrocarbon group, a is an integer of 1-3, b is an integer of 0-3. A + b is not more than 5. When b is 2 or more, a plurality of R ² may be the same or different.   The substrate processing according to claim 22, wherein a content ratio of the structural unit represented by the formula (1-1) is 20 mol% or more and 90 mol% or less with respect to all the structural units constituting the polymer. Method.   The method for processing a substrate according to any one of claims 14 to 23, wherein a thickness of the resist film in the resist film forming step is 7 µm or more and 20 µm or less.   The substrate processing method according to any one of claims 14 to 24, wherein the radiation used in the exposure step is KrF excimer laser light. The solvent includes a first solvent having a viscosity at 20 ° C. of 1.5 mPa · s or less,
The substrate processing method according to any one of claims 19 to 25, wherein a content of the first solvent in all the solvents is 60 mass% or more.