JP2015199847A - Production method of polymer for lithography, production method of resist composition, and method for manufacturing patterned substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polymer for lithography with high reproducibility, in which solubility in a solvent can be improved, productivity of the polymer is improved with a reduced process pass time while suppressing a thermal history imparted to the polymer, and thereby, more stable qualities can be obtained.SOLUTION: A production method of a polymer for lithography is provided, which includes: a polymerization step of radically polymerizing a monomer by use of a polymerization initiator in the presence of a polymerization solvent to obtain a polymerization solution; and a recovery step of supplying a solution containing the polymer obtained in the above polymerization step to a solvent that is a poor solvent with respect to the polymer, so as to crystallize the polymer and to obtain a precipitate. In the recovery step, temperatures of the solution including the polymer and of the poor solvent are each controlled within a fluctuation width of ±5.0°C; and the recovery step satisfies the expression (1) (solid content weight (g) of the polymer in the polymerization solvent)/((volume (L) of the poor solvent)×(mixing time (minutes) of the polymerization solvent with the poor solvent))≤2.0.

Description

  The present invention relates to a method for producing a lithography polymer, a method for producing a resist composition using the lithography polymer obtained by the production method, and a substrate on which a pattern is formed using the resist composition. Regarding the method.

  In recent years, a resist pattern formed in a manufacturing process of a semiconductor element, a liquid crystal element, or the like has been rapidly miniaturized due to progress in lithography technology. As a technique for miniaturization, there is a reduction in wavelength of irradiation light. Specifically, the irradiation light has become shorter from conventional ultraviolet rays typified by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm) to shorter wavelength DUV (Deep Ultra Violet). .

  Recently, KrF excimer laser (wavelength: 248 nm) lithography technology has been introduced, and ArF excimer laser (wavelength: 193 nm) lithography technology and EUV (wavelength: 13.5 nm) lithography technology for further shortening the wavelength have been studied. . Furthermore, these immersion lithography techniques are also being studied. Also, as a different type of lithography technology, electron beam lithography technology has been energetically studied.

A “chemically amplified resist composition” containing a photoacid generator has been proposed as a highly sensitive resist composition used for forming a resist pattern using the irradiation light or electron beam of the short wavelength. Improvement and development of amplification resist compositions are underway.
For example, as a chemically amplified resist polymer used in ArF excimer laser lithography, an acrylic polymer that is transparent with respect to light having a wavelength of 193 nm has attracted attention. As the acrylic polymer, for example, a polymer of (meth) acrylic acid ester having an adamantane skeleton in an ester portion and (meth) acrylic acid ester having a lactone skeleton in an ester portion has been proposed (Patent Document 1). etc).

  In general, in a conventional method for producing a polymer for lithography, a method of adding a polymerization reaction solution after polymerization reaction to a poor solvent to precipitate the polymer, and isolating and purifying the polymer is known (patent) Literature 2-5). However, in the conventional method, when the polymerization reaction solution is added to a poor solvent, if the addition rate is too high, a slurry in which a uniform polymer is precipitated cannot be obtained, process passability is deteriorated, and the polymer performance is stable. Furthermore, there was a problem that the reproducibility such as the quality of the polymer between each production lot could not be obtained.

JP-A-10-313595 JP 2005-320444 A JP 2009-138053 A Japanese Patent Laid-Open No. 2003-020212 JP 2008-013733 A

  The present invention has been made in view of the above matters, and by defining the relationship between the volume of the poor solvent and the dropping time to the poor solvent with respect to the weight of the solid content of the polymer in the polymerization reaction solution, It has been found that the solubility in a solvent can be improved while suppressing the heat history applied to the polymer, and a stable quality polymer can be produced with good reproducibility by shortening the process passage time.

In order to solve the above problems, a method for producing a lithographic polymer of the present invention comprises a polymerization step of radically polymerizing a monomer to obtain a polymerization reaction solution using a polymerization initiator in the presence of a polymerization solvent. A solution containing the polymer obtained by the polymerization step is supplied to a poor solvent for the polymer, and a solution step is performed in which the polymer is precipitated to obtain a precipitate. And the temperature of the poor solvent is controlled within a fluctuation range of ± 5.0 ° C., and further satisfies the following formula (1).
Weight of solid content of polymer in polymerization reaction solution (g) / (poor solvent capacity (L) × mixing time of polymerization reaction solution with poor solvent (min)) ≦ 2.0 Formula (1)

  The present invention provides the method for producing a polymer for lithography, wherein the temperature of the solution containing the polymer and the poor solvent are controlled using a container provided with a jacket.

  In the present invention, the process for producing a lithography polymer by the method for producing a lithography polymer of the present invention, and the resulting lithography polymer are mixed with a compound that generates an acid upon irradiation with actinic rays or radiation. A method for producing a resist composition is provided.

  The present invention includes a step of producing a resist composition by the method for producing a resist composition of the present invention, a step of coating the obtained resist composition on a work surface of a substrate to form a resist film, and the resist Provided is a method for manufacturing a substrate on which a pattern is formed, which includes a step of exposing a film and a step of developing the exposed resist film using a developer.

According to the production method of the present invention, it is possible to purify efficiently, and to obtain a polymer solution for lithography having a stable polymer performance with few impurities with good reproducibility.
This also improves the reproducibility of resist performance such as sensitivity and development contrast when a lithographic polymer is used in the resist composition.
According to the substrate manufacturing method of the present invention, a highly accurate fine resist pattern can be stably formed using a resist composition having excellent resist performance such as sensitivity and development contrast.

<Polymer for lithography>
The polymer for lithography of the present invention preferably has a structural unit having a polar group.
[Structural unit having a polar group]
The “polar group” is a group having a polar functional group or a polar atomic group. Specific examples include a hydroxy group, a cyano group, an alkoxy group, a carboxy group, an amino group, a carbonyl group, and a fluorine atom. A group containing a sulfur atom, a group containing a lactone skeleton, a group containing an acetal structure, a group containing an ether bond, and the like.
Among these, the resist polymer applied to the pattern forming method that is exposed to light having a wavelength of 250 nm or less preferably has a structural unit having a lactone skeleton as the structural unit having a polar group, It is preferable to have a structural unit having a functional group.

(Constitutional unit / monomer having a lactone skeleton)
Examples of the lactone skeleton include a lactone skeleton having about 4 to 20 members. The lactone skeleton may be a monocycle having only a lactone ring, or an aliphatic or aromatic carbocyclic or heterocyclic ring may be condensed with the lactone ring.
In the case where the polymer contains a structural unit having a lactone skeleton, the content thereof is preferably 20 mol% or more, more preferably 25 mol% or more of all structural units (100 mol%) from the viewpoint of adhesion to a substrate or the like. Is more preferable. Moreover, from the point of a sensitivity and resolution, 60 mol% or less is preferable, 55 mol% or less is more preferable, and 50 mol% or less is further more preferable.

As a monomer having a lactone skeleton, a (meth) acrylic acid ester having a substituted or unsubstituted δ-valerolactone ring, a substituted or unsubstituted γ-butyrolactone ring is used because of its excellent adhesion to a substrate or the like. Preferably, at least one selected from the group consisting of monomers having it is preferred, and monomers having an unsubstituted γ-butyrolactone ring are particularly preferred.
In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acryloyloxy” means acryloyloxy or methacryloyloxy.

Specific examples of the monomer having a lactone skeleton include β- (meth) acryloyloxy-β-methyl-δ-valerolactone, 4,4-dimethyl-2-methylene-γ-butyrolactone, β- (meth) acryloyl. Oxy-γ-butyrolactone, β- (meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolactone, 2- (1- (meth) acryloyloxy) ethyl-4-butanolide , (Meth) acrylic acid pantoyl lactone, 5- (meth) acryloyloxy-2,6-norbornanecarbolactone, 8-methacryloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3 - one, 9-methacryloxy-4-oxatricyclo [5.2.1.0 ^{2, 6]} cited decan-3-one and the like . Examples of the monomer having a similar structure include methacryloyloxysuccinic anhydride.
Monomers having a lactone skeleton may be used alone or in combination of two or more.

(Structural unit / monomer having a hydrophilic group)
The “hydrophilic group” in the present specification is at least one of —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a methoxy group, a carboxy group, and an amino group.
Among these, it is preferable that the resist polymer applied to the pattern forming method exposed to light having a wavelength of 250 nm or less has a hydroxy group or a cyano group as a hydrophilic group.
The content of the structural unit having a hydrophilic group in the polymer is preferably from 5 to 30 mol%, more preferably from 10 to 25 mol%, of the total structural units (100 mol%) from the viewpoint of the resist pattern rectangularity. .

  Examples of the monomer having a hydrophilic group include a (meth) acrylic acid ester having a terminal hydroxy group; a derivative having a substituent such as an alkyl group, a hydroxy group, or a carboxy group on the hydrophilic group of the monomer; Monomers having a cyclic hydrocarbon group (for example, cyclohexyl (meth) acrylate, 1-isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylic acid) Dicyclopentyl, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, etc.) having a hydrophilic group such as a hydroxy group or a carboxy group as a substituent; Can be mentioned.

  Specific examples of the monomer having a hydrophilic group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy- (meth) acrylate. -Propyl, 4-hydroxybutyl (meth) acrylate, 3-hydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl-2-adamantyl (meth) acrylate, etc. Is mentioned. From the point of adhesion to a substrate or the like, 3-hydroxyadamantyl (meth) acrylate, 3,5-dihydroxyadamantyl (meth) acrylate, 2- or 3-cyano-5-norbornyl (meth) acrylate, 2-cyanomethyl- 2-adamantyl (meth) acrylate and the like are preferable. The monomer which has a hydrophilic group may be used individually by 1 type, and may be used in combination of 2 or more type.

[Constitutional unit having acid leaving group]
When the polymer for lithography of the present invention is used for resist applications, it is preferable to have a structural unit having an acid-eliminable group in addition to the above-mentioned structural unit having a polar group. The structural unit may be further included.
The “acid leaving group” is a group having a bond that is cleaved by an acid, and a part or all of the acid leaving group is removed from the main chain of the polymer by cleavage of the bond.
In the resist composition, a polymer having a structural unit having an acid-eliminable group reacts with an acid component to become soluble in an alkaline solution, and has an effect of enabling resist pattern formation.
The proportion of the structural unit having an acid leaving group is preferably 20 mol% or more, more preferably 25 mol% or more, out of all the structural units (100 mol%) constituting the polymer from the viewpoint of sensitivity and resolution. . Moreover, 60 mol% or less is preferable from the point of the adhesiveness to a board | substrate etc., 55 mol% or less is more preferable, and 50 mol% or less is further more preferable.

The monomer having an acid leaving group may be any compound having an acid leaving group and a polymerizable multiple bond, and known ones can be used. The polymerizable multiple bond is a multiple bond that is cleaved during the polymerization reaction to form a copolymer chain, and an ethylenic double bond is preferable.
Specific examples of the monomer having an acid leaving group include (meth) acrylic acid esters having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and having an acid leaving group. It is done. The alicyclic hydrocarbon group may be directly bonded to an oxygen atom constituting an ester bond of (meth) acrylic acid ester, or may be bonded via a linking group such as an alkylene group.
The (meth) acrylic acid ester has an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and a tertiary carbon atom at the bonding site with the oxygen atom constituting the ester bond of the (meth) acrylic acid ester. A (meth) acrylic acid ester having an alicyclic group or an alicyclic hydrocarbon group having 6 to 20 carbon atoms and a -COOR group (R may have a substituent) on the alicyclic hydrocarbon group. (Meth) acrylic acid ester in which a tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group is bonded directly or via a linking group is included.

In particular, in the case of producing a resist composition that is applied to a pattern forming method that is exposed to light having a wavelength of 250 nm or less, as a preferred example of a monomer having an acid leaving group, for example, 2-methyl-2- Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 1- (1′-adamantyl) -1-methylethyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl ( Examples include meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, isopropyl adamantyl (meth) acrylate, 1-ethylcyclooctyl (meth) acrylate, and the like.
As the monomer having an acid leaving group, one type may be used alone, or two or more types may be used in combination.

The polymer for lithography in the present invention (hereinafter sometimes simply referred to as polymer) is not particularly limited as long as it is a polymer used in the lithography process. For example, a resist polymer used for forming a resist film, an antireflection film (TARC) formed on the upper layer of the resist film, or a reflection used for forming an antireflection film (BARC) formed on the lower layer of the resist film. Examples thereof include a polymer for prevention film, a gap fill film polymer used for forming a gap fill film, and a polymer for top coat film used for forming a top coat film.
Examples of the resist polymer include a copolymer containing one or more of the structural units having the acid-eliminable group and one or more of the structural units having the polar group.

Examples of the polymer for antireflection film include a structural unit having a light-absorbing group and an amino group, an amide group, a hydroxyl group, an epoxy group, etc. that can be cured by reacting with a curing agent to avoid mixing with the resist film. And a copolymer containing a structural unit having a reactive functional group. The light-absorbing group is a group having high absorption performance with respect to light in a wavelength region where the photosensitive component in the resist composition is sensitive. Specific examples include an anthracene ring, naphthalene ring, benzene ring, quinoline ring. , A group having a ring structure (optionally substituted) such as a quinoxaline ring and a thiazole ring. In particular, when KrF laser light is used as irradiation light, an anthracene ring or an anthracene ring having an arbitrary substituent is preferable, and when ArF laser light is used, a benzene ring or a benzene having an arbitrary substituent A ring is preferred.
Examples of the optional substituent include a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxy group, a carbonyl group, an ester group, an amino group, and an amide group. Among these, those having a protected or unprotected phenolic hydroxyl group as the light absorbing group are preferable from the viewpoint of good developability and high resolution. Examples of the structural unit / monomer having the light-absorbing group include benzyl (meth) acrylate and p-hydroxyphenyl (meth) acrylate.

Examples of polymers for gap fill films are reactive functionalities that have a suitable viscosity for flowing into narrow gaps and can be cured by reacting with curing agents to avoid mixing with resist films and antireflection films. Examples thereof include a copolymer containing a structural unit having a group, specifically, a copolymer of hydroxystyrene and a monomer such as styrene, alkyl (meth) acrylate, or hydroxyalkyl (meth) acrylate.
Examples of the polymer for the topcoat film used in immersion lithography include a copolymer containing a structural unit having a carboxyl group, a copolymer containing a structural unit having a fluorine-containing group substituted with a hydroxyl group, and the like.

<Method for producing polymer>
The method for producing a lithography polymer of the present invention generally includes a polymerization step of polymerizing monomers to obtain a polymerization reaction solution, and a recovery step of depositing a polymer from the polymerization reaction solution to obtain a precipitate.
[Polymerization process]
A solution polymerization method is used as the polymerization method. That is, a polymerization reaction solution is obtained by radical polymerization of a monomer using a polymerization initiator in the presence of a polymerization solvent.
In the solution polymerization method, the monomer and the polymerization initiator may be supplied to the polymerization vessel either continuously or dropwise. As a solution polymerization method, a monomer and a polymerization initiator are dropped into a polymerization vessel from the viewpoint that a variation in average molecular weight and molecular weight distribution due to differences in production lots is small and a reproducible polymer can be easily obtained. The dropping polymerization method is preferred.

In the dropping polymerization method, the inside of the polymerization vessel is heated to a predetermined polymerization temperature, and then the monomer and the polymerization initiator are dropped into the polymerization vessel independently or in any combination.
A monomer may be dripped only with a monomer, and may be dripped as a monomer solution which melt | dissolved the monomer in the polymerization solvent.
A polymerization solvent and / or monomer may be charged into the polymerization vessel in advance.
The polymerization initiator may be dissolved directly in the monomer, may be dissolved in the monomer solution, or may be dissolved only in the polymerization solvent.
The monomer and the polymerization initiator may be dropped into the polymerization vessel after mixing in the same storage tank; they may be dropped into the polymerization container from each independent storage tank; They may be mixed immediately before the supply and dropped into the polymerization vessel.
One of the monomer and the polymerization initiator may be dropped first, and then the other may be dropped with a delay, or both may be dropped at the same timing.
The dropping rate may be constant until the end of dropping, or may be changed in multiple stages according to the consumption rate of the monomer or the polymerization initiator.
The dripping may be performed continuously or intermittently.
The polymerization temperature is preferably 50 to 150 ° C.
After a polymerization reaction at a predetermined polymerization temperature for a predetermined time, the polymerization reaction is stopped to obtain a polymerization reaction solution. As a method for stopping the polymerization reaction, a process of cooling the reaction solution is generally used, but it can also be stopped by adding a radical scavenger.

Examples of the polymerization solvent include the following.
Ethers: chain ether (diethyl ether, propylene glycol monomethyl ether, etc.), cyclic ether (tetrahydrofuran (hereinafter referred to as “THF”), 1,4-dioxane, etc.) and the like.
Esters: methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”), γ-butyrolactone, and the like.
Ketones: acetone, methyl ethyl ketone (hereinafter referred to as “MEK”), methyl isobutyl ketone (hereinafter referred to as “MIBK”), cyclohexanone, and the like.
Amides: N, N-dimethylacetamide, N, N-dimethylformamide and the like.
Sulfoxides: dimethyl sulfoxide and the like.
Aromatic hydrocarbons: benzene, toluene, xylene and the like.
Aliphatic hydrocarbon: hexane and the like.
Alicyclic hydrocarbons: cyclohexane and the like.
A polymerization solvent may be used individually by 1 type, and may use 2 or more types together.

As the polymerization initiator, those that generate radicals efficiently by heat are preferable. For example, an azo compound (2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] etc.
), Organic peroxides (2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, di (4-tert-butylcyclohexyl) peroxydicarbonate, etc.).

[Recovery process]
A polymer solution containing the polymer obtained in the polymerization step is mixed with a poor solvent to precipitate the polymer to obtain a precipitate. This technique is called a reprecipitation method, and is effective for removing unreacted monomers, polymerization initiators and the like remaining in the polymerization reaction solution. If the unreacted monomer remains as it is, the sensitivity decreases when used as a resist composition, so it is preferable to remove it as much as possible. The monomer content as an impurity in the polymer obtained by the production method of the present invention is more preferably 2.0% by mass or less, further preferably 1.0% by mass or less, and particularly preferably 0.29% by mass or less. 0.25% by mass or less is most preferable.

  The poor solvent is a solvent that has a small ability to dissolve the target polymer and from which the polymer can precipitate. According to the composition of the polymer, known ones can be appropriately selected and used. Methanol, isopropyl alcohol, diisopropyl ether, heptane, or water is preferable because unreacted monomers, polymerization initiators, and the like used in the lithography polymer can be efficiently removed. A poor solvent may be used individually by 1 type, and may use 2 or more types together.

  In the recovery step, the polymerization reaction solution is preferably dropped into a poor solvent to precipitate the polymer in the polymerization reaction solution. The amount of the poor solvent when the polymerization reaction solution is dropped into the poor solvent is not particularly limited, but is preferably equal to or more than that of the diluted solution in terms of easier reduction of unreacted monomers, and is 3 on a mass basis. Is preferably 4 times or more, more preferably 4 times or more, still more preferably 5 times or more, and particularly preferably 6 times or more. The upper limit is not particularly limited, but if it is too much, the working efficiency in the subsequent filtration step is deteriorated. For example, 10 times or less is preferable on a mass basis.

  In the recovery step, the concentration of the polymer solution containing the polymer obtained in the polymerization step mixed with the poor solvent is not particularly limited, but is preferably 10% by mass to 60% by mass from the viewpoints of productivity and handleability. 15 mass% to 50 mass% is still more preferable.

In the recovery step, it is preferable to control the temperature of the polymer solution and the poor solvent so as to be the desired temperatures. As a method of temperature control, use a container with a temperature-controllable jacket so that the internal temperature becomes the desired temperature so that it is not affected by the outside temperature due to the season or day and night. It is preferable to change and control. It is better to increase the heat retaining effect by covering the jacket with a heat insulating material or the like. In addition, when the polymer solution and the poor solvent container are connected by a pipe or a tube, it is preferable to keep the connected portion warm by using a heat insulating material.
The control temperature of each solution is not particularly limited, but is preferably 0 ° C. to 60 ° C. from the viewpoint of influence on the polymer and the boiling point of the solvent, and more preferably 20 ° C. to 50 ° C. from the point of impurity removal. At this time, from the viewpoint of improving the reproducibility of the molecular weight and the residual monomer amount, it is preferable to adjust the temperature within ± 5.0 ° C., and to adjust the temperature within ± 3.0 ° C. with respect to the desired temperature. Is more preferable, and it is more preferable to adjust the temperature within ± 1.0 ° C.

The method for producing a polymer of the present invention satisfies the following formula (1) in the recovery step for obtaining the precipitate.
Weight of solid content of polymer in polymerization reaction solution (g) / (poor solvent capacity (L) × mixing time of polymerization reaction solution with poor solvent (min)) ≦ 2.0 Formula (1)
In the present invention, the upper limit of the formula (1) is 2.0 or less, but 1.9 or less is preferable, 1.5 or less is more preferable in order to better exhibit the effects of the present invention. 0 or less is more preferable.
The lower limit of the above formula (1) is not particularly limited, but the amount of the poor solvent used is not excessive, the mixing time is not excessively long, and the production efficiency is preferably 0.01 or more, preferably 0.05 or more. Is more preferable, and 0.1 or more is more preferable.

In the present invention, the “mixing time of the polymerization reaction solution with the poor solvent” in the above formula (1) is required for mixing the solution containing the polymer and the poor solvent in order to precipitate the polymer. It's time.
For example, when dropping a poor solvent into a polymer solution containing a polymer, it is the dropping time of the poor solvent into the polymer solution, and when dropping a polymer solution containing the polymer into the poor solvent. Is the dropping time of the polymer solution into the product solvent.

Before mixing the polymerization reaction solution with the poor solvent, the polymerization reaction solution may be diluted to an appropriate solution viscosity with a diluent solvent, if necessary. Examples of the dilution solvent include 1,4-dioxane, acetone, THF, MEK, MIBK, γ-butyrolactone, PGMEA, PGME, and ethyl lactate. These may use 1 type and may use 2 or more types together.
When performing dilution, the difference between the solubility parameter (hereinafter also referred to as SP value) of the solvent (mixture of polymerization solvent and dilution solvent) in the diluted polymerization reaction solution and the SP value of the poor solvent used for reprecipitation is The smaller one is preferable in that good dispersibility of the polymer can be obtained and the monomer can be efficiently removed.
The SP value of the solvent can be determined, for example, by the method described in “Polymer Handbook”, 4th edition, pages VII-675 to VII-711. Specifically, Table 1 (VII- 683), Tables 7 to 8 (VII-688 to VII-711). Further, the SP value in a mixed solvent of a plurality of solvents can be determined by a known method. For example, the SP value of the mixed solvent can be obtained as the sum of products of the SP value of each solvent and the volume fraction, assuming that additivity is established.

In the recovery step, the target polymer is obtained in the form of a wet powder by filtering the precipitate deposited in the poor solvent.
Alternatively, the target polymer precipitate can be obtained by repeating the operation of dispersing the filtered wet powder again in a poor solvent and then filtering it. This process is referred to as “librarian” and is effective for further reducing impurities such as unreacted monomers and polymerization initiator remaining in the wet powder.
From the viewpoint that the polymer can be obtained while maintaining high productivity, it is preferable to recover the polymer precipitate only by the reprecipitation method without performing the rethrowing.

[Drying process]
In this invention, it can obtain as a powder by drying the deposit obtained at the collection | recovery process.

Any drying method may be used as long as the wet powder can be dried to have a predetermined solid content, and a known drying method can be used. A vacuum drying method in which the pressure is reduced under a dry atmosphere, a heat drying method in which the heat is dried in a dry atmosphere, or a vacuum heat drying method in which the pressure is reduced and heated in a dry atmosphere is preferable, particularly in terms of drying in a shorter time. The method is preferred.
The degree of pressure reduction when the pressure is reduced is preferably 50 kPa or less, more preferably 40 kPa or less, and further preferably 30 kPa or less. The lower limit value of the degree of decompression is not particularly limited, but is practically 0.01 kPa or more.
When heating, the heating temperature is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and further preferably 40 ° C. or higher. The upper limit of the heating temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower in terms of preventing thermal deterioration of the polymer.

[Dissolution process]
The polymer wet powder obtained in the recovery step or the polymer powder obtained in the drying step may be dissolved in a good solvent as necessary. Thereby, a solution in which the target polymer is dissolved in a good solvent is obtained.
As the good solvent, a known solvent capable of dissolving the target polymer can be used, and the solvents mentioned above as the polymerization solvent can be used. When the target polymer is used for the production of a resist composition, the same solvent as the resist solvent in the resist composition is preferably used as a good solvent in the dissolution step.
In the present invention, dissolving in a good solvent at room temperature means dissolving in a good solvent that has reached a constant temperature at a predetermined room temperature (atmospheric temperature) without performing active cooling or heating. The room temperature (atmosphere temperature) is 0 to 40 ° C, preferably 16 to 30 ° C.
It is preferable that the temperature of the fine dry powder immediately before mixing the fine dry powder with a good solvent reaches a constant temperature at the predetermined room temperature (atmosphere temperature). In other words, the absolute value of the temperature difference between the finely-dried powder to be mixed and the good solvent is preferably smaller in that it does not require active cooling or heating. Specifically, the absolute value of the temperature difference is preferably 20 ° C. or less, and more preferably 15 ° C. or less.
Further, when the fine dry powder is dissolved in a good solvent, additives such as a storage stabilizer may be added as appropriate. That is, the polymer solution may contain an additive such as a storage stabilizer.

[Concentration process]
The solution obtained in the dissolving step may be concentrated to obtain a concentrated solution in which the target polymer is dissolved in a good solvent. By performing the concentration, the remaining low-boiling compounds can be removed.
A known concentration method can be used. It is preferable to concentrate under reduced pressure because it can be concentrated in a short time. The degree of reduced pressure in the case of concentration under reduced pressure is preferably 50 kPa or less, more preferably 40 kPa or less, and further preferably 30 kPa or less. The lower limit value of the degree of decompression is not particularly limited, but is actually 0.05 kPa or more.
In addition, heating during vacuum concentration is also preferable because it can be concentrated in a short time. As heating temperature, 20 degreeC or more is preferable, 30 degreeC or more is more preferable, and 40 degreeC or more is further more preferable. In addition, the heating temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower in terms of preventing thermal degradation of the polymer.
During the concentration, it is preferable to carry out stirring while preventing bumping. In addition, it is preferable to concentrate in a pressure-resistant metal reaction vessel in that pressure control is possible and heat conductivity is excellent and reaction temperature control is facilitated. As the metal, stainless steel (hereinafter also referred to as SUS) is preferable because it has high corrosion resistance and can reduce the mixing of metal impurities into the polymer.

[Filtering process]
The solution obtained in the dissolution step or the concentrate obtained in the concentration step may be filtered as necessary. As a result, a polymer solution with reduced polymer gel and foreign matter can be obtained.
In view of the fact that the pressure loss before and after the filtration filter can be kept low and the filtration can be performed in a short time, it is preferable to filter the solution obtained in the dissolution step before the concentration step.
In terms of efficiently reducing polymer gels and foreign substances that may be mixed into the final product, it is preferable to filter the obtained concentrated solution after the concentration step.
Both the solution obtained in the dissolving step and the concentrated solution may be filtered. That is, after filtering the solution obtained in the dissolution step, the obtained filtrate may be subjected to the concentration step and concentrated, and the resulting concentrated solution may be further filtered.

<Method for producing resist composition>
The method for producing a resist composition of the present invention comprises a step of producing a target polymer by the production method of the present invention, and the resulting polymer and a compound that generates an acid upon irradiation with actinic rays or radiation. Process. If necessary, a resist solvent is further added and mixed. As the resist solvent, the solvents listed above as the polymerization solvent can be used. The resist composition thus obtained is a chemically amplified resist composition.
The polymer used in the production of the resist composition may be the solution obtained in the dissolution step, the filtrate filtered thereafter, the concentrate obtained in the concentration step, or the filtrate filtered thereafter.

[Compound that generates acid upon irradiation with actinic ray or radiation]
The compound that generates an acid upon irradiation with actinic rays or radiation can be arbitrarily selected from those that can be used as a photoacid generator for a chemically amplified resist composition. A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinone diazide compounds, diazomethane compounds, and the like.
0.1-20 mass parts is preferable with respect to 100 mass parts of polymers, and, as for the usage-amount of a photo-acid generator, 0.5-10 mass parts is more preferable.

[Nitrogen-containing compounds]
The chemically amplified resist composition may contain a nitrogen-containing compound. By including the nitrogen-containing compound, the resist pattern shape, the stability over time, and the like are further improved. That is, the cross-sectional shape of the resist pattern becomes closer to a rectangle, and the resist film is irradiated with light, then baked (PEB), and then left for several hours before the next development process. Although it is a line, the occurrence of the deterioration of the cross-sectional shape of the resist pattern is further suppressed when left as such (timed).
The nitrogen-containing compound is preferably an amine, more preferably a secondary lower aliphatic amine or a tertiary lower aliphatic amine.
As for the quantity of a nitrogen-containing compound, 0.01-2 mass parts is preferable with respect to 100 mass parts of polymers.

[Organic carboxylic acid, phosphorus oxo acid or derivative thereof]
The chemically amplified resist composition may contain an organic carboxylic acid, an oxo acid of phosphorus, or a derivative thereof (hereinafter collectively referred to as an acid compound). By including an acid compound, it is possible to suppress deterioration in sensitivity due to the blending of the nitrogen-containing compound, and further improve the resist pattern shape, stability with time of leaving, and the like.
Examples of the organic carboxylic acid include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid.
Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid or derivatives thereof, phosphonic acid or derivatives thereof, phosphinic acid or derivatives thereof, and the like.
The amount of the acid compound is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymer.

[Additive]
The resist composition may contain various additives such as a surfactant, other quenchers, sensitizers, antihalation agents, storage stabilizers, and antifoaming agents as necessary. Any additive can be used as long as it is known in the art. Further, the amount of these additives is not particularly limited, and may be determined as appropriate.

<Manufacturing method of substrate on which fine pattern is formed>
An example of the manufacturing method of the board | substrate with which the fine pattern was formed of this invention is demonstrated.
First, the resist composition obtained by the production method of the present invention is applied to the surface of a substrate to be processed such as a silicon wafer on which a desired fine pattern is to be formed by spin coating or the like. And the resist film is formed on a board | substrate by drying the to-be-processed board | substrate with which this resist composition was apply | coated by baking process (prebaking) etc.

Next, the resist film is irradiated with light having a wavelength of 250 nm or less through a photomask to form a latent image (exposure). As irradiation light, a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, and an EUV excimer laser are preferable, and an ArF excimer laser is particularly preferable. Moreover, you may irradiate an electron beam.
In addition, immersion in which light is irradiated with a high refractive index liquid such as pure water, perfluoro-2-butyltetrahydrofuran, or perfluorotrialkylamine interposed between the resist film and the final lens of the exposure apparatus. Exposure may be performed.

After exposure, heat treatment is appropriately performed (post-exposure baking, PEB), an alkali developer is brought into contact with the resist film, and the exposed portion is dissolved in the developer and removed (development). Examples of the alkaline developer include known ones.
After development, the substrate is appropriately rinsed with pure water or the like. In this way, a resist pattern is formed on the substrate to be processed.

The substrate on which the resist pattern is formed is appropriately heat-treated (post-baked) to strengthen the resist and selectively etch the portion without the resist.
After the etching, the resist is removed with a release agent to obtain a substrate on which a fine pattern is formed.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, “part” in each example and comparative example means “part by mass” unless otherwise specified. The measurement method and evaluation method used the following methods.
In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. It may be a range defined by a combination of values of the following examples or values of the examples.

<Measurement of weight average molecular weight>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined in terms of polystyrene by gel permeation chromatography under the following conditions (GPC conditions).
[GPC conditions]
Equipment: Tosoh Corporation, Tosoh High Speed GPC Equipment HLC-8220GPC (trade name),
Separation column: manufactured by Showa Denko, Shodex GPC K-805L (trade name) connected in series,
Measurement temperature: 40 ° C.
Eluent: Tetrahydrofuran (THF)
Sample: A solution in which about 20 mg of a polymer is dissolved in 5 mL of THF and filtered through a 0.5 μm membrane filter.
Flow rate: 1 mL / min,
Injection volume: 0.1 mL,
Detector: differential refractometer.

Calibration curve I: About 20 mg of standard polystyrene was dissolved in 5 mL of THF, and the solution was filtered through a 0.5 μm membrane filter and injected into a separation column under the above conditions, and the relationship between elution time and molecular weight was determined. As the standard polystyrene, the following standard polystyrene manufactured by Tosoh Corporation (both trade names) were used.
F-80 (Mw = 706,000),
F-20 (Mw = 190,000),
F-4 (Mw = 37,900),
F-1 (Mw = 10,200),
A-2500 (Mw = 2,630),
A-500 (mixture of Mw = 682, 578, 474, 370, 260).

<Evaluation of residual solvent>
The residual solvent in the polymer was determined by an internal standard method by gas chromatography under the following conditions (GC conditions).
[GC condition]
Apparatus: Agilent Technologies, Inc., Agilent Technologies 6890 (trade name),
Carrier gas: He,
Total flow rate: 24 mL / min,
Separation column: HP-INNWAX (trade name), manufactured by Agilent Technologies, Inc., length 30 m × inner diameter 0.32 mm × film thickness 0.25 μm,
Column flow rate: 1.5 mL / min (40 ° C.)
Column heating conditions: 50 ° C. (holding for 10 minutes) → (heating at 10 ° C./min)→110° C. (holding for 9 minutes),
Inlet temperature: 230 ° C
Detection port temperature: 230 ° C.
Detector: Hydrogen flame ionization detector (FID)
Injection volume: 1 μL
Sample: 0.1 mL of the polymer was added with 5 mL of acetonitrile and allowed to stand at 25 ° C. for 12 hours. Then, 0.98 mL of the supernatant was collected, and 20 μL of 1% solution of n-butyl alcohol as an internal standard was collected. Added solution.

<Evaluation of resist composition>
[Sensitivity and development contrast measurement]
The resist composition was spin-coated on a 6-inch silicon wafer and prebaked (PAB) at 120 ° C. for 60 seconds on a hot plate to form a thin film having a thickness of 300 nm. Using an ArF excimer laser exposure apparatus (product name: VUVES-4500, manufactured by RISOTEC Japan), 18 shots of 10 mm × 10 mm ² were exposed while changing the exposure amount. Then, after post-baking (PEB) at 110 ° C. for 60 seconds, 2.38 mass% tetramethylammonium hydroxide at 23 ° C. using a resist development analyzer (product name: RDA-800). Development was performed with an aqueous solution for 65 seconds, and the change with time in the resist film thickness during development at each exposure amount was measured.

[analysis]
A curve plotting the logarithm of the exposure amount (mJ / cm ² ) and the residual film thickness ratio (hereinafter referred to as the residual film ratio) (%) when developed for 60 seconds with respect to the initial film thickness, based on the obtained data (Hereinafter, exposure amount-residual film rate curve) was prepared, and Eth sensitivity (required exposure amount for setting the residual film rate to 0%, which represents sensitivity) was determined as follows. It shows that the sensitivity of a resist composition is so high that the value of Eth sensitivity is small.
Eth sensitivity: exposure amount (mJ / cm ² ) at which the exposure amount-residual film rate curve intersects with a residual film rate of 0%.

<Example 1>
[Polymerization process]
242.0 g of ethyl lactate was placed in a 1 L SUS flask equipped with a nitrogen inlet, a stirrer, a condenser, a dropping funnel, a jacket, and a thermometer. The inside of the flask was replaced with nitrogen, the flask was placed in a hot water bath while maintaining the nitrogen atmosphere, and the temperature of ethyl lactate in the flask was raised to 80 ° C. while stirring the inside of the flask.
Thereafter, the following mixture 1 was dropped into the flask over 4 hours from the dropping funnel, and the temperature of 80 ° C. was further maintained for 3 hours.
Then, the reaction liquid in a flask was cooled to 25 degreeC, the polymerization reaction was stopped, and the polymerization reaction solution was obtained.
[Mixture 1]
102.00 g of a monomer of the following formula (m1),
117.60 g of a monomer of the following formula (m2),
70.80 g of a monomer of the following formula (m3),
435.6 g of ethyl lactate,
Dimethyl-2,2'-azobisisobutyrate (Wako Pure Chemical Industries, V601 (trade name)) 8.280 g.
The charging ratio (mol%) of each monomer is (m1) / (m2) / (m3) = 40/40/20
It is.

[Recovery Step] Hereinafter, the recovery step divides the polymerization reaction solution obtained in the polymerization step, and room temperature environment of 15.0 ° C., 20.0 ° C., 22.5 ° C., 25.0 ° C., 27.5 ° C. Each was done below.
Put 97.63 g (solid content: 29.29 g) of the polymerization reaction solution (30% by mass) obtained in the polymerization step into a 1 L SUS flask equipped with a jacket and a thermometer, and keep the temperature constant at 25 ° C. The jacket temperature was set and the temperature was controlled.
0.75 L of a mixed solvent of methanol and water (methanol / water = 75/25 volume ratio) as a poor solvent is placed in another 1 L flask made of SUS equipped with a jacket and a thermometer, and becomes a constant 25 ° C. The jacket temperature was set to control the temperature.
From the flask containing the polymerization reaction solution, the poor solvent was added dropwise to the flask containing the poor solvent over 40 minutes while stirring the poor solvent using a pump to precipitate a polymer (white precipitate). After heating to 40 ° C. and holding for 30 minutes, the mixture was cooled to 25 ° C. and the precipitate was filtered off to obtain 49.7 g of wet powder.

  Next, the entire amount of the obtained wet powder was mixed with the poor solvent (0.75 L) again. As a poor solvent, a mixed solvent of methanol and water (methanol / water = 85/15 volume ratio) was used. The mixture was heated to 40 ° C. with stirring and held for 30 minutes, then cooled to 25 ° C. and the precipitate was filtered off to obtain 45.5 g of a wet powder.

[Dissolution process]
In an atmosphere at 25 ° C., 25.0 g of the wet powder obtained above was dissolved in 150.0 g of PGMEA (25 ° C.). Subsequently, the obtained solution was filtered with a filter made of nylon having a pore size of 0.02 μm.

[Concentration process]
The obtained filtrate was concentrated under the conditions of a pressure of 20 kPa and a temperature of 50 ° C., and when the distillate no longer appeared, the pressure was changed to 3 kPa and a temperature of 65 ° C. Concentration was performed until
About the obtained concentrate (PGMEA solution), the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn), and the amount of residual ethyl lactates were measured by said method. Table 1 shows each result and three times the standard deviation (3σ).

[Evaluation of resist composition]
A resist composition was prepared using the obtained concentrated liquid. That is, to 400 parts of the concentrated solution, 2 parts of triphenylsulfonium triflate as a photoacid generator is added, and further PGMEA as a solvent is added so that the polymer concentration becomes 12.5% by mass and mixed. After preparing a uniform solution, the solution was filtered through a membrane filter having a pore size of 0.1 μm to obtain a resist composition. Eth sensitivity and γ value of the obtained resist composition were measured by the above methods. Each result and three times the standard deviation (3σ) are shown in Table 1.

<Example 2>
In the recovery step, a polymer was produced and evaluated in the same manner as in Example 1 except that the temperature was controlled by setting the jacket temperature so that the polymerization reaction solution was kept constant at 35 ° C. The results are shown in Table 1.
<Example 3>
In the recovery step, a polymer was produced and evaluated in the same manner as in Example 2 except that the jacket temperature of the polymerization reaction solution was set to 34.5 ° C and the jacket temperature of the poor solvent solution was set to 25.0 ° C. . The results are shown in Table 1.

<Comparative Example 1>
In the recovery step, a polymer was produced in the same manner as in Example 1 except that the polymerization reaction solution was placed in a 1 L SUS flask without a jacket, and the internal temperature of the polymerization reaction solution was not controlled, and evaluation was performed. did. The results are shown in Table 1.

<Comparative Example 2>
In the recovery step, a polymer was produced and evaluated in the same manner as in Example 1 except that a poor solvent was placed in a 1 L SUS flask without a jacket and the internal temperature of the poor solvent was not controlled. The results are shown in Table 1.

<Comparative Example 3>
In the recovery step, each of the polymerization reaction solution and the poor solvent was put in another 1 L SUS flask without a jacket, and the polymer was prepared in the same manner as in Example 1 except that the internal temperature was not controlled. Manufactured and evaluated. The results are shown in Table 1.

From the above results, the method according to the present invention (Examples 1 to 3) reproduces a lithography polymer having good reproducibility of molecular weight and impurity amount and excellent resist performance in terms of the sensitivity of the resist composition. It was confirmed that it can be obtained with good performance.
On the other hand, in the case of the method different from the present invention (Comparative Examples 1 to 3), the reproducibility of the molecular weight and the impurity amount is poor, and the reproducibility of the sensitivity of the resist composition using this is also compared with the above Examples 1 to 3. Inferiority was confirmed.

Claims (4)

In the presence of the polymerization solvent, using a polymerization initiator, radical polymerization of the monomer to obtain a polymerization reaction solution, a solution containing the polymer obtained by the polymerization step, a poor solvent for the polymer And a recovery step of precipitating the polymer to obtain a precipitate, and in the recovery step, each temperature of the solution containing the polymer and the poor solvent is controlled within a fluctuation range of ± 5.0 ° C., Furthermore, the manufacturing method of the polymer for lithography which satisfies following formula (1).
Weight of solid content of polymer in polymerization reaction solution (g) / (poor solvent capacity (L) × mixing time of polymerization reaction solution with poor solvent (min)) ≦ 2.0 Formula (1) The method for producing a polymer for lithography according to claim 1, wherein the temperature of the solution containing the polymer and the poor solvent are controlled by using a container provided with a jacket.   A step of producing a lithographic polymer by the production method according to claim 1, and a step of mixing the obtained lithographic polymer with a compound that generates an acid upon irradiation with actinic rays or radiation. A method for producing a resist composition. A step of producing a resist composition by the production method according to claim 3, a step of applying the obtained resist composition on a work surface of a substrate to form a resist film, and the resist film, A method for producing a substrate on which a pattern is formed, comprising a step of exposing and a step of developing the exposed resist film using a developer.