JP5500795B2 - RESIST MATERIAL, RESIST COMPOSITION, AND METHOD FOR MANUFACTURING SUBSTRATE WITH MICRO PATTERN - Google Patents

Description

The present invention relates to a resist material , a resist composition, and a method for manufacturing a substrate on which a fine pattern is formed.

  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 excimer laser (wavelength: 13 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 high-resolution 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). 2).

By the way, since the multi-component polymer obtained by polymerizing two or more types of monomers is different in structure and reaction rate of each monomer, it is included in the polymer to be produced in the early polymerization stage and the late polymerization stage. The proportion of structural units derived from each monomer is different, that is, the proportion of the structural units varies for each polymer chain contained in the polymer. In addition, the molecular weight distribution is widened.
A polymer with a large variation in the proportion of structural units for each polymer chain and a wide molecular weight distribution is not sufficiently soluble in a solvent (hereinafter referred to as a resist solvent) when preparing a resist composition. Further, when the polymer is used for a resist composition, there is a problem in solubility in a developing solution, and therefore defects (development defects) occur. Further, the line edge roughness of the resist pattern is increased.

A resist composition containing a polymer having a small variation in the proportion of structural units for each polymer chain has been proposed (Patent Documents 3 and 4). However, even in the case of the polymer, the above-mentioned problem has not been sufficiently solved because the variation in the proportion of structural units for each polymer chain is not sufficiently small and the molecular weight distribution is wide.
JP 10-319595 A JP-A-10-274852 JP 2004-355023 A JP 2007-269907 A

  The present invention is a polymer excellent in solubility in a resist solvent; a resist composition capable of forming a resist pattern with few defects and low line edge roughness; and a highly accurate fine pattern with few defects. A method is provided by which a substrate can be manufactured.

The resist material of the present invention uses a reactor having a flow path, continuously supplies a monomer component, a polymerization initiator, and a solvent from the start end of the flow path. N types including a structural unit having a polar group and a structural unit having an acid-eliminable group, obtained by a polymer production method in which a polymer is obtained by radical polymerization to discharge a polymer solution from the end of the flow path. (Wherein n is an integer of 2 or more). The resist polymer (P), wherein the structural unit having the polar group is a structural unit having a lactone skeleton or —C (CF ₃ ) A structural unit having at least one hydrophilic group selected from the group consisting of _2- OH, hydroxy group, cyano group, methoxy group, carboxy group and amino group, and having the acid-eliminable group However, it has 6 to 2 carbon atoms A (meth) acrylic acid ester having a alicyclic hydrocarbon group of 0 and having a tertiary carbon atom at the bonding site with the oxygen atom constituting the ester bond of the (meth) acrylic acid ester, or 6 carbon atoms -20 cycloaliphatic hydrocarbon group and -COOR group (R is an optionally substituted tertiary hydrocarbon group, tetrahydrofuranyl group, tetrahydropyranyl group) Group or an oxepanyl group) is a structural unit derived from a (meth) acrylic ester bonded directly or via a linking group , and each structural unit (Ui) in the polymer (P) (however, i is an integer from 1 to n. a ratio X _{Ui (mol%))} of the weight average molecular weight contained in the polymer by size exclusion chromatography (P) (Mw) more than molecular weight of The body (PH) is fractionated into m fractions (where m is an integer of 4 or more) and the polymer (PHj) contained in each fraction fractionated (where j is 1 to m) The ratio X _Uij (mol%) of each structural unit (Ui) in (is an integer) comprises a resist polymer that satisfies the following formula (1).
0.95 ≦ X _Uij / X _Ui ≦ 1.05 (1 )

The resist composition of the present invention includes the resist material of the present invention.
The method for producing a substrate having a fine pattern according to the present invention comprises a step of applying the resist composition of the present invention on a substrate to be processed to form a resist film, and applying light having a wavelength of 250 nm or less to the resist film. The method includes a step of forming a latent image by irradiation and a step of developing the resist film on which the latent image is formed with a developer.

The polymer of the present invention is excellent in solubility in a resist solvent.
According to the resist composition of the present invention, a resist pattern with few defects and small line edge roughness can be formed.
According to the method for manufacturing a substrate on which a fine pattern is formed according to the present invention, it is possible to manufacture a substrate on which a highly accurate fine pattern with few defects is formed.

  In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid.

<Polymer (P)>
The polymer of the present invention is a polymer (P) composed of n types of structural units (where n is an integer of 2 or more) including a structural unit having a polar group and a structural unit having an acid leaving group. It is. The polymer of this invention may contain 2 or more types of structural units which have a polar group, and may contain 2 or more types of structural units which have an acid leaving group.

The mass average molecular weight (Mw) of the polymer (P) is preferably 1000 or more, more preferably 2000 or more, and still more preferably 3000 or more, from the viewpoints of dry etching resistance and resist pattern shape.
The mass average molecular weight (Mw) of the polymer (P) is preferably 10,000 or less, more preferably 8000 or less, and still more preferably 6000 or less, from the viewpoint of solubility in a resist solvent and resolution.

  The ratio Mw / Mn of the mass average molecular weight (Mw) and the number average molecular weight (Mw) of the polymer (P) is preferably 1.0 to 1.8 from the viewpoint of solubility in a resist solvent and resolution. 0 to 1.7 is more preferable, and 1.0 to 1.6 is more preferable.

A ratio X _Ui (mol%) of each structural unit (Ui) (where i is an integer of 1 to n) in the polymer (P) and contained in the polymer (P) by size exclusion chromatography. A polymer (PHj) contained in each fraction obtained by dividing a polymer (PH) having a molecular weight of not less than mass average molecular weight (Mw) into m fractions (where m is an integer of 4 or more). ) (Where j is an integer from 1 to m), the ratio X _Uij (mol%) of each structural unit (Ui) satisfies the following formula (1).
0.95 ≦ X _Uij / X _Ui ≦ 1.05 (1).

That is, in all the fractions (1 to m), all of the structural units (U1 to Un) satisfy the formula (1).
Therefore, when two or more structural units having a polar group are present, each of the structural units having two or more polar groups satisfies Formula (1) in all fractions (1 to m). Further, when there are two or more structural units having an acid leaving group, in all fractions (1 to m), each of the structural units having two or more acid leaving groups is represented by the formula (1). Satisfied.

  The higher the molecular weight of the polymer, the lower the solubility in the resist solvent. Therefore, the variation in the proportion of structural units for each polymer chain contained in the polymer having a large molecular weight greatly affects the solubility in the resist solvent. On the other hand, in a polymer having a small molecular weight, the solubility in a resist solvent is not greatly affected even if the variation in the proportion of constituent units of each polymer chain contained in the polymer increases. Therefore, in the polymer (PH) having a molecular weight equal to or higher than the mass average molecular weight (Mw), the dispersion of the proportion of the structural units for each polymer chain is reduced, that is, by satisfying the formula (1), the resist of the whole polymer The solubility with respect to the working solvent will be improved.

  Examples of size exclusion chromatography include gel permeation chromatography (hereinafter referred to as GPC) in which the mobile phase is an organic solvent, or gel filtration chromatography in which the mobile phase is an aqueous solution, and the solubility of the polymer in the mobile phase. From this point, GPC is preferable.

The weight average molecular weight (Mw) of the polymer (P), the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mw), the ratio X _{Ui of} each structural unit (Ui), and each of the polymer (PHj) The ratio X _Uij of the structural unit (Ui) is obtained by the following procedures (i) to (v).

Procedure (i):
The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer (P) are determined, and the ratio thereof, that is, Mw / Mn is determined.
A mass average molecular weight (Mw) and a number average molecular weight (Mn) are the polystyrene conversion values calculated | required by GPC on the following GPC conditions I.

[GPC condition I]
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 (hereinafter referred to as THF),
Sample: A solution in which about 20 mg of the polymer (P) was 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: A solution obtained by dissolving about 20 mg of standard polystyrene in 5 mL of THF and filtering through a 0.5 μm membrane filter is injected into a separation column under the above conditions, and the relationship between elution time and molecular weight is determined. Standard polystyrene (all trade names) manufactured by Tosoh Corporation are used as standard polystyrene.
F-80 (Mw = 706000),
F-20 (Mw = 19000),
F-4 (Mw = 37900),
F-1 (Mw = 10200),
A-2500 (Mw = 2630),
A-500 (mixture of Mw = 682, 578, 474, 370, 260).

Step (ii):
The GPC condition is changed to GPC condition II, and a standard curve II (relation between elution time and molecular weight) is obtained using standard polystyrene.

[GPC condition II]
Equipment: Tosoh Corporation, Tosoh High Speed GPC Equipment HLC-8220GPC (trade name),
Preparative column: Showa Denko Co., Shodex GPC K-2005 (trade name) connected in series,
Measurement temperature: 40 ° C.
Eluent: THF,
Sample: A solution in which about 120 mg of polymer (P) was dissolved in 5 mL of THF and filtered through a 0.5 μm membrane filter,
Flow rate: 4 mL / min,
Injection volume: 1 mL,
Detector: differential refractometer,
Calibration curve II: About 120 mg of standard polystyrene is dissolved in 5 mL of THF and injected into a preparative column under the above conditions using a solution filtered through a 0.5 μm membrane filter, and the relationship between elution time and molecular weight is determined. Standard polystyrene (all trade names) manufactured by Tosoh Corporation are used as standard polystyrene.
F-80 (Mw = 706000),
F-20 (Mw = 19000),
F-4 (Mw = 37900),
F-1 (Mw = 10200),
A-2500 (Mw = 2630),
A-500 (mixture of Mw = 682, 578, 474, 370, 260).

Step (iii):
In the calibration curve II, the elution time T at which the molecular weight is Mw determined in the procedure (i) is determined.

Step (iv):
The polymer (P) solution was injected into the preparative column, and the time from the elution start of the polymer to the elution time T determined in step (iii) under GPC condition II was equally divided into m and eluted at each time. Each component is collected as a polymer (PHj) solution to obtain m fractions. m is an integer greater than or equal to 4, 4-50 are preferable and 5-30 are especially preferable.

Step (v):
Ratio _{X Ui} and _{X Uij} of the respective structural units (Ui) ^is determined by ¹ H-NMR measurement in the case where it can be determined by the 1 H-NMR measurement, it is determined by the ¹ H-NMR measurement by such overlapping proton peak When it is not possible, it is determined by ¹³ C-NMR measurement.

[The ¹ H-NMR measurement]
¹ H-NMR measurement was performed using JSX Corporation GSX-400 type FT-NMR (trade name), about 5% by mass of polymer (P) or polymer (PHj) solution (deuterated chloroform solution). Alternatively, a deuterated dimethyl sulfoxide solution) is put into a test tube having a diameter of 5 mmφ, and the measurement is carried out 64 times in an observation frequency of 400 MHz and a single pulse mode. The measurement temperature is 40 ° C. when deuterated chloroform is used as the solvent, and 60 ° C. when deuterated dimethyl sulfoxide is used as the solvent.

[ ¹³ C-NMR measurement]
^{The 13} C-NMR measurement was performed by using UNITY-INOVA type FT-NMR (trade name) manufactured by Varian Technologies, Inc., about 20% by mass of polymer (P) or polymer (PHj) deuterated dimethyl sulfoxide. The solution is put into a test tube having a diameter of 5 mmφ, and the measurement is performed at a total temperature of 50,000 times by the proton complete decoupling method in which the measurement temperature is 60 ° C., the observation frequency is 125 MHz, and the nuclear overhauser effect (NOE) is removed.

(Constitutional unit having a polar group)
A structural unit having both a polar group and an acid leaving group is classified as a structural unit having a polar group.
Examples of the structural unit having a polar group include a structural unit having a lactone skeleton and a structural unit having a hydrophilic group.

(Constitutional unit 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.

Examples of the structural unit having a lactone skeleton include a structural unit derived from a monomer having a lactone skeleton, and a structural unit derived from an acrylic monomer having a lactone skeleton is 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.

  Monomers having a lactone skeleton include β-methacryloyloxy-β-methyl-δ-valerolactone, 4,4-dimethyl-2-methylene-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, β-methacryloyl. Examples thereof include oxy-β-methyl-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, 2- (1-methacryloyloxy) ethyl-4-butanolide, and pantoyllactone methacrylate. Examples of the monomer having a similar structure include methacryloyloxysuccinic anhydride. As the monomer having a lactone skeleton, α-methacryloyloxy-γ-butyrolactone (hereinafter referred to as GBLMA) is preferable from the viewpoint of adhesion of the polymer to the substrate.

Monomers having a lactone skeleton may be used alone or in combination of two or more.
The proportion of the structural unit having a lactone skeleton is preferably 30 mol% or more and more preferably 35 mol% or more in the total structural units (100 mol%) of the polymer (P) from the viewpoint of adhesion to a substrate or the like. . 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.

(Structural unit having a hydrophilic group)
The “hydrophilic group” 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.

Examples of the structural unit having a hydrophilic group include a structural unit derived from a monomer having a hydrophilic group, and a structural unit derived from an acrylic monomer having a hydrophilic group is preferable.
As the monomer having a hydrophilic group, for example, 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 (cyclohexyl (meth) acrylate, 1-isobornyl (meth) acrylate, adamantyl (meth) acrylate), tricyclodecanyl (meth) acrylate, dimethacrylate (meth) acrylate Cyclopentyl, 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.

  Examples of the monomer having a hydrophilic group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-n-propyl (meth) acrylate, Examples thereof include 4-hydroxybutyl (meth) acrylate and 3-hydroxyadamantyl methacrylate, and 1-methacryloyloxy-3-hydroxyadamantane (hereinafter referred to as HAdMA) is preferable from the viewpoint of adhesion to a substrate or the like. .

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.
The proportion of the structural unit having a hydrophilic group is preferably 5 to 30 mol%, more preferably 10 to 25 mol% in the total structural unit (100 mol%) of the polymer (P) from the viewpoint of the resist pattern rectangularity. preferable.

(Structural unit having an acid leaving group)
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.
When used as a resist composition, the polymer (P) having a structural unit having an acid-eliminable group is soluble in an alkali by an acid, and has the effect of enabling the formation of a resist pattern.

Examples of the structural unit having an acid leaving group include a structural unit derived from a monomer having an acid leaving group, and a structural unit derived from an acrylic monomer having an acid leaving group is preferable. .
As the monomer having an acid leaving group, for example, a (meth) acryl having an alicyclic hydrocarbon group having 6 to 20 carbon atoms and a group capable of leaving by the action of an acid. Acid ester etc. are mentioned. 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.

Examples of the monomer having an acid leaving group include 2-methyl-2-adamantyl methacrylate (hereinafter referred to as MAdMA), 2-ethyl-2-adamantyl methacrylate and the like.
As the monomer having an acid labile group, one type may be used alone, or two or more types may be used in combination.
The proportion of the structural unit having an acid labile group is preferably 20 mol% or more, and more preferably 25 mol% or more in the total structural units (100 mol%) of the polymer (P) 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 polymer (P) may contain other structural units other than the structural unit having a polar group and the structural unit having an acid leaving group, as necessary.

<Method for producing polymer (P)>
As the method for producing the polymer (P), the following production method is preferable from the viewpoint that a variation in the proportion of structural units for each polymer chain is small, a polymer having a small mass average molecular weight and a narrow molecular weight distribution can be easily obtained. .

Using a reactor having a flow path, a monomer component, a polymerization initiator and a solvent are continuously supplied from the beginning of the flow path, and the monomer component is radically polymerized in the flow path to obtain a polymer. In the method for producing a polymer, in which the polymer solution is discharged from the end of the flow path, the monomer component includes a monomer having a polar group and a monomer having an acid leaving group, The 5-minute half-life temperature of the polymerization initiator is 60 to 120 ° C., and the flow path has a region where the temperature is equal to or higher than the 5-minute half-life temperature. Time is 5 to 60 minutes, The manufacturing method of the polymer characterized by the above-mentioned.
Residence time (min) = volume of channel in the region (mL) / feed rate of monomer component, polymerization initiator and solvent to the channel (mL / min)

(Reactor)
FIG. 1 is a schematic configuration diagram showing an example of a reactor used in a method for producing a polymer. The reactor 1 includes a flow path 2; a heating means 3 for heating the middle of the flow path 2; a cooling means 4 for cooling the middle of the flow path 2 on the downstream side of the heating means 3; A supply means 5 connected; and a recovery container 6 installed at the end of the flow path 2.

The flow path 2 is supplied with a monomer component, a polymerization initiator and a solvent from the start end, and discharges the polymer solution from the end end.
Examples of the form of the flow path 2 include a tube and a groove. Examples of the cross-sectional shape of the tube include a circle, an ellipse, a triangle, a quadrangle, and a hexagon. A circle is preferable. What is necessary is just to determine suitably the dimension (inner diameter in the case of a circle) of the cross section of a pipe | tube so that the range of the cross-sectional area mentioned later may be satisfied. The width and depth of the groove may be appropriately determined so as to satisfy the range of the cross-sectional area described later.
In addition, the number of the flow paths 2 may be one or plural. Moreover, the several flow path 2 may be merged in the middle, and the one flow path 2 may be branched into several in the middle.

The flow path 2 has the area | region (R) made into the temperature beyond the 5-minute half life temperature of the below-mentioned polymerization initiator. This area | region (R) is a reaction area | region where the polymerization reaction of a monomer component is performed.
What is necessary is just to determine suitably the length of the flow path 2 in an area | region (R) according to the stay time etc. which are mentioned later, and is 0.1-100 m normally.

Cross-sectional area per one channel 2 in the region (R) is preferably 1.0 × ¹⁰ -4 ~1.0cm ^2, more preferably ^{5.0 × 10 -4 ~0.25cm 2, 1} . 0 × 10 ^{−3 to} 4.0 × 10 ⁻² cm ² is particularly preferable. When the cross-sectional area exceeds 1.0 cm ² , a temperature distribution is generated in the region (R), and a polymer having a small molecular weight distribution and a small variation in the proportion of structural units for each polymer chain cannot be obtained. When the cross-sectional area is less than 1.0 × 10 ⁻⁴ cm ² , pressure loss such as clogging of the flow path increases, resulting in a failure in feeding the raw material.

The flow path 2 has the area | region (C) which is a cooling area | region for stopping a polymerization reaction downstream from an area | region (R).
The length of the flow path 2 in the region (C) may be a length that can sufficiently cool the polymer solution, and is usually 0.1 to 10 m.
The cross-sectional area of the channel 2 in the region (C) may be approximately the same as the cross-sectional area of the channel in the region (R).

  In the case where there are a plurality of supply means 5, each of the flow paths 2 is supplied from each supply means downstream from the merging point of the plurality of flow paths 2 extending from each supply means and upstream from the region (R). It has the area | region (M) which is a mixing area | region which mixes a liquid.

The length of the flow path 2 in the region (M) may be a length that can sufficiently mix the liquids, and is usually 0.1 to 10 m.
The cross-sectional area of the flow channel 2 in the region (M) may be approximately the same as the cross-sectional area of the flow channel 2 in the region (R).
Moreover, when there are two or more supply means, the mixer 7 may be provided at a junction of a plurality of flow paths 2 extending from each supply means.

The heating means 3 heats the temperature of the region (R) to a predetermined temperature.
Examples of the heating means 3 include an oil bath, a ribbon heater, and a mantle heater.
The heating means 3 preferably has a temperature adjusting means for keeping the temperature of the region (R) at a predetermined temperature. Examples of the temperature adjustment means include a thermometer, a heater, and a control device that adjusts the output of the heater based on temperature information from the thermometer.

The cooling means 4 cools the temperature of the region (C) to a predetermined temperature.
Examples of the cooling means 4 include an ice bath, a water bath, a circulation type cooler, and the like.

The supply means 5 supplies a monomer component, a polymerization initiator, and a solvent to the start end of the flow path 2.
Examples of the supply unit 5 include a syringe pump, a plunger pump, a tube pump, and a diaphragm pump.
The supply means 5 may consist of one supply means or a plurality of supply means. From the point of suppressing the polymerization reaction in the supply means 5, the first supply means 5a for supplying the liquid containing the monomer component in the solvent or the liquid containing the monomer component without the solvent and the polymerization in the solvent What consists of the 2nd supply means 5b which supplies the liquid containing an initiator is preferable.

The collection container 6 collects the polymer solution discharged from the end of the flow path 2.
The collection container is preferably cooled by a cooling means.

(Production conditions)
In order to obtain the polymer (P), it is necessary that the polymerization initiator is efficiently decomposed to generate radicals and the monomer components are polymerized in a short time. For this purpose, using a polymerization initiator having a half-life temperature of 60 to 120 ° C. for 5 minutes, the residence time is 5 to 60 minutes in the region (R) maintained at a temperature of 5 minutes or more half-life temperature. It is necessary to polymerize.

  The temperature of the region (R) is not less than the 5-minute half-life temperature of the polymerization initiator, and preferably not less than the 5-minute half-life temperature + 10 ° C. The temperature in the region (R) is preferably 140 ° C. or lower, and more preferably 120 ° C. or lower. When the temperature of the region (R) is equal to or higher than the 5-minute half-life temperature of the polymerization initiator, a polymer having a small variation in the proportion of structural units for each polymer chain and a narrow molecular weight distribution can be obtained in a high yield. Can do. Further, if the temperature of the region (R) is 140 ° C. or lower, the thermal decomposition of the polymer can be suppressed, so that it is easy to obtain a polymer having a sufficiently narrow molecular weight distribution.

The stay time (namely, reaction time) calculated | required from the following formula in area | region (R) needs to be 5 to 60 minutes.
If the residence time is 5 minutes or more, the polymerization initiator is efficiently decomposed, sufficient radicals are generated, the variation in the proportion of constituent units for each polymer chain is small, the mass average molecular weight is small, and the molecular weight distribution A narrow polymer is obtained. When the residence time is within 60 minutes, the polymerization time can be shortened and the productivity is improved.

Residence time (min) = volume of the channel 2 in the region (R) (mL) / feed rate of the monomer component, polymerization initiator and solvent to the channel 2 (mL / min).
In the formula, the supply rate of the monomer component, the polymerization initiator and the solvent is the supply rate of the liquid containing the polymerization initiator and the solvent in the solvent when the supply means 5 is one. In this case, it is the sum of the supply rate of the liquid containing the monomer component in the solvent or the liquid containing the monomer component without the solvent and the supply rate of the liquid containing the polymerization initiator in the solvent.

The temperature of the region (C) is preferably 10 ° C. or less, and more preferably 0 ° C. or less. The temperature of the region (C) is preferably equal to or higher than the freezing point of the solvent.
The residence time of the polymer solution in the region (C) may be a time that can sufficiently cool the polymer solution, and is usually 0.5 to 10 minutes.

0-30 degreeC is preferable and, as for the temperature of an area | region (M), 5-25 degreeC is more preferable.
The residence time of each liquid in the region (M) may be a time during which each liquid can be sufficiently mixed, and is usually 1 to 20 minutes.

The supply rate of the monomer component, the polymerization initiator and the solvent to the flow path 2 is preferably 8 × 10 ^{−6 to} 1000 mL / min, and more preferably 3 × 10 ^{−5 to} 1.0 mL / min.

(Monomer component)
The monomer component may contain other monomers other than the monomer having a polar group and the monomer having an acid leaving group, as necessary.
The proportion of the monomer component is preferably from 10 to 50 mass%, more preferably from 10 to 30 mass%, out of a total of 100 mass% of the monomer component, the polymerization initiator, and the solvent. When the proportion of the monomer component is 10% by mass or more, the temperature distribution in the region (R) becomes uniform, and a polymer having a narrower molecular weight distribution can be produced. When the proportion of the monomer component is 50% by mass or less, the viscosity of the liquid containing the polymer does not become too high, and clogging of the flow path 2 is suppressed.

(Polymerization initiator)
As the polymerization initiator, one having a 5-minute half-life temperature of 60 to 120 ° C is used. When the 5-minute half-life temperature is 60 ° C. or higher, the polymerization initiator is efficiently decomposed to generate radicals, increase the reaction rate, reduce the variation in the proportion of structural units for each polymer chain, and have a molecular weight distribution. Narrower polymers can be produced. If the 5-minute half-life temperature is 120 ° C. or lower, the temperature of the region (R) is kept low, and the polymer does not decompose.
The 5-minute half-life temperature is a temperature at which the decomposition rate of the polymerization initiator becomes 50% in 5 minutes. The 5-minute half-life temperature can be determined from the reaction rate constant, Arrhenius equation, based on the 10-hour half-life temperature of the polymerization initiator and the activation energy.

  As a polymerization initiator having a 5-minute half-life temperature of 60 to 120 ° C., dimethyl 2,2′-azobis (2-methylpropionate) (5-minute half-life temperature: 107 ° C., hereinafter referred to as V-601). ), 2,2′-azobis (2,4-dimethylvaleronitrile) (5-minute half-life temperature: 90 ° C., hereinafter referred to as V-65), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile) (5-minute half-life temperature: 66 ° C.), 2,2′-azobisisobutyronitrile (5-minute half-life temperature: 104 ° C.), and the like.

  0.1-30 mol% is preferable with respect to 100 mol% of a monomer component, and, as for the quantity of a polymerization initiator, 1-25 mol% is more preferable.

(solvent)
Examples of the solvent include chain ethers (diethyl ether, propylene glycol monomethyl ether, etc.), cyclic ethers (THF, 1,4-dioxane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, Butyl lactate, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), γ-butyrolactone, etc., ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane) Etc.).

(Other ingredients)
Chain transfer agents may be used. Examples of chain transfer agents include 1-butanethiol, 2-butanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1-propanethiol, 2-hydroxyethyl mercaptan, and the like. Can be mentioned.

(Post-processing)
The obtained polymer (P) solution is diluted to a suitable solution viscosity with a good solvent, if necessary, and then dropped into a large amount of a poor solvent (methanol, water, hexane, heptane, etc.) to obtain a polymer. It is preferable to deposit (P). This process is called reprecipitation, and is very effective for removing unreacted monomers, polymerization initiators and the like remaining in the polymer (P) solution. If these unreacted substances remain as they are, there is a possibility that the performance of the resist film may be adversely affected. The reprecipitation process may be unnecessary depending on circumstances.

Thereafter, the precipitate is filtered off and sufficiently dried to obtain the polymer (P). Moreover, after filtering off, you may use it as a wet powder, without drying.
Further, the polymer (P) solution may be used as it is as a resist composition, or the polymer (P) solution may be diluted with an appropriate solvent and used as a resist composition, and the polymer (P) solution is concentrated. And may be used as a resist composition. At that time, additives such as a storage stabilizer may be appropriately added.

<Resist composition>
The resist composition of the present invention is obtained by dissolving the polymer of the present invention in a solvent. When the resist composition of the present invention is used as a chemically amplified resist composition, a photoacid generator is further dissolved.

(solvent)
Examples of the solvent include the same solvents as used for the production of the polymer.

(Photoacid generator)
The photoacid generator can be arbitrarily selected from those that can be used as the photoacid generator of the 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 quantity 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 its derivative)
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 of the present invention may contain various additives such as surfactants, 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 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 the 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.

The polymer of the present invention described above has a small mass average molecular weight, a narrow molecular weight distribution, and a small variation in the proportion of constituent units for each polymer chain contained in the polymer having a molecular weight larger than the mass average molecular weight. Excellent solubility in resist solvent.
Moreover, since the resist composition using the polymer of the present invention has high solubility in a developing solution, a resist pattern with few defects can be formed. Further, a resist pattern having a small line edge roughness can be formed.
Further, by using the resist composition of the present invention, a highly accurate fine resist pattern with few defects can be stably formed.
Therefore, the polymer and resist composition of the present invention can be suitably used for DUV excimer laser lithography or electron beam lithography, particularly lithography using ArF excimer laser (193 nm).

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.
Further, the polymer and the resist composition were evaluated as follows.

Number average molecular weight (Mn), mass average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymer (P), ratio X _{Ui of} each structural unit (Ui), and each structural unit (Ui) of polymer (PHj) ) Ratio X _Uij was determined by the above procedures (i) to (v). However, the number m of fractions was 6.

[Example 1]
The reactor shown in FIG. 2 was used as the reactor. The reactor 10 includes a first syringe pump 12 (supplying unit) in which a liquid containing a monomer component is filled in a solvent; and a second syringe pump 14 in which a liquid containing a polymerization initiator is filled in the solvent. (Supply means); first supply pipe 16 (flow path) extending from the first syringe pump 12; second supply pipe 18 (flow path) extending from the second syringe pump 14; first supply A T-shaped tube 20 (flow path) provided at a junction between the pipe 16 and the second supply pipe 18; a reaction tube 22 (flow path) extending from the T-shaped tube 20; An oil bath 24 (heating means); a first ice bath 26 (cooling means) that cools the middle of the reaction tube 22 downstream of the oil bath 24; and a polymer solution discharged from the reaction tube 22 is recovered. Measuring cylinder 28 (collection container); second ice for cooling measuring cylinder 28 And a 30 (cooling means).

The reaction tube 22 (flow path) is in a region (M) where the liquid containing the monomer component merged in the T-shaped tube 20 and the liquid containing the polymerization initiator are mixed; and downstream of the region (M) A region (R) in which the monomer component is polymerized by being heated in the oil bath 24 (that is, a region immersed in the oil bath 24); And a region (C) in which the polymerization reaction is stopped by being cooled in the ice bath 26 (that is, a region immersed in the first ice bath 26).
The reaction tube 22 is bent spirally in the region (M) and the region (R).

The material of the first supply pipe 16, the second supply pipe 18, the T-shaped pipe 20, and the reaction pipe 22 is stainless steel (SUS316).
The length and inner diameter of the first supply pipe 16 and the second supply pipe 18 are as follows. The inner diameter of the T-shaped tube 20 is as follows. The length of the reaction tube 22 in each region, and the cross-sectional area and volume of the hollow portion of the reaction tube 22 in the region (R) are as follows.
Each supply pipe: length 0.5m, inner diameter 0.5mm,
T-shaped tube: Inner diameter, 0.5mm,
Region (M): length 5 m, inner diameter 0.5 mm,
Region (R): length 10 m, inner diameter 0.5 mm, hollow cross-sectional area 0.0020 cm ² , volume 2.0 mL,
Region (C): length 0.5 m, inner diameter 1.0 mm.

  The oil bath 24 has a temperature controller 32 (temperature adjusting means). The temperature controller 32 includes a thermometer 34 and a heater 36, and adjusts the output of the heater 36 based on temperature information from the thermometer 34.

GBLMA 5.9 g, MAdMA 8.1 g, HAdMA 4.1 g, and ethyl lactate 13.7 g are mixed and dissolved while stirring, and nitrogen bubbling is carried out for 5 minutes or more. A liquid containing was prepared.
0.7 g of V-65 (5-minute half-life temperature: 90 ° C.) was dissolved in 30.3 g of ethyl lactate, nitrogen bubbling was performed for 5 minutes or more, and a liquid containing a polymerization initiator in a solvent was prepared. .
The ratio of the monomer component was 30% by mass out of 100% by mass in total of the monomer component, the polymerization initiator, and the solvent.
A liquid containing a monomer component in a solvent was filled in the microsyringe of the first syringe pump 12 under a nitrogen atmosphere.
A liquid containing a polymerization initiator in a solvent was filled in the microsyringe of the second syringe pump 14 under a nitrogen atmosphere.

The temperature of the oil bath 24 was heated to 100 ° C., and the temperature of the region (R) was maintained at 100 ° C.
The first syringe pump 12 was operated, and a liquid containing a monomer component in the solvent was continuously supplied to the first supply pipe 16 at a supply rate of 0.049 mL / min.
At the same time, the second syringe pump 14 was operated, and a liquid containing a polymerization initiator in the solvent was continuously supplied to the second supply pipe 18 at a supply rate of 0.049 mL / min.
Residence time in region (R) was 20 minutes.

90 minutes after the start of the supply of each solution, the measuring cylinder 28 was replaced, sampling of the polymer solution was started, and 62.48 g of the polymer solution was recovered in 10 hours.
The obtained polymer solution was added dropwise to a mixed solvent of about 10 times the amount of methanol and water (methanol / water = 80/20 volume ratio) with stirring to precipitate a white precipitate (polymer (P1)). Obtained. The precipitate was filtered off and again poured into a mixed solvent of methanol and water in the same amount as above (methanol / water = 90/10 volume ratio), and the precipitate was washed with stirring. And the precipitate after washing | cleaning was separated by filtration, and polymer wet powder was obtained. 10 g of the polymer wet powder was dried at 40 ° C. under reduced pressure for about 40 hours. The obtained polymer (P1) was evaluated. The results are shown in Tables 1 and 2.

The remaining polymer wet powder was poured into 88,000 parts of PGMEA, completely dissolved, and then passed through a nylon filter having a pore diameter of 0.04 μm (P-NYLON N66FILTER 0.04M (trade name) manufactured by Nippon Pole Co., Ltd.). The polymer solution was filtered.
The polymer solution was heated under reduced pressure to distill off methanol and water, and further PGMEA was distilled off to obtain a polymer (P1) solution having a polymer concentration of 25% by mass. At this time, the maximum ultimate vacuum was 0.7 kPa, the maximum solution temperature was 65 ° C., and the distillation time was 8 hours.

  400 parts of the polymer (P1) solution, 2 parts of triphenylsulfonium triflate as a photoacid generator, and PGMEA as a solvent were mixed so that the polymer concentration was 12.5% by mass. 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.

[Comparative Example 1]
Under a nitrogen atmosphere, 73.1 g of ethyl lactate was placed in a 500 mL flask (1), and the temperature of the hot water bath was raised to 80 ° C. while stirring.
In a separate 500 mL flask (2), mix 28.56 g of GBLMA, 39.31 g of MAdMA, 19.84 g of HAdMA, 10.63 g of V-601 and 131.5 g of ethyl lactate until there is no solids. It melt | dissolved with stirring and implemented nitrogen bubbling for 5 minutes or more, and prepared the raw material liquid. This was dropped into the flask (1) at a constant rate over 4 hours, and then kept at a temperature of 80 ° C. for 3 hours. During the dropping, the temperature of the flask (1) was kept at 80 ° C.

About the obtained polymer solution, operation similar to Example 1 was performed and the polymer (P2) was obtained. The evaluation results of the polymer (P2) are shown in Tables 1 and 3.
Moreover, operation similar to Example 1 was performed using the polymer (P2), and the polymer (P2) solution was obtained. Moreover, operation similar to Example 1 was performed using the polymer (P2) solution, and the resist composition was obtained.

<Evaluation of resist composition>
The resist composition of Example 1 or Comparative Example 1 was spin coated on a silicon wafer and pre-baked at 120 ° C. for 60 seconds using a hot plate to form a resist film having a thickness of 0.3 μm. The resist film was exposed with an ArF excimer laser having a wavelength of 193 nm through a mask, and then subjected to post-exposure baking at 120 ° C. for 60 seconds using a hot plate. Subsequently, it developed at room temperature using the 2.38 mass% tetramethylammonium hydroxide aqueous solution, wash | cleaned with the pure water, and dried, and the resist pattern was formed.
The line edge roughness and defect of the resist pattern, and the line and space pattern of 0.20 μm were compared with those of Example 1 and Comparative Example 1.
As a result, when the polymer (P1) of Example 1 was used, the line edge roughness and the defect were excellent, and a 0.20 μm line and space pattern was obtained clearly and accurately. On the other hand, when the polymer (P2) of Comparative Example 1 was used, the line edge roughness and the defect were poor, and the pattern was not clear.

  The resist composition using the polymer of the present invention can be suitably used for DUV excimer laser lithography, these immersion lithography and electron beam lithography, particularly ArF excimer laser lithography, and this immersion lithography.

It is a schematic block diagram which shows an example of the reactor used with the manufacturing method of a polymer. It is a figure which shows the reactor used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reactor 2 Flow path 10 Reactor 16 1st supply pipe (flow path)
18 Second supply pipe (flow path)
20 T-shaped tube (flow path)
22 Reaction tube (flow path)

Claims (3)

Using a reactor having a flow path, a monomer component, a polymerization initiator and a solvent are continuously supplied from the beginning of the flow path, and the monomer component is radically polymerized in the flow path to obtain a polymer. And n kinds of structural units having a polar group and an acid-eliminable group obtained by a method for producing a polymer, wherein a polymer solution is discharged from the end of the flow path (where n is 2 or more) A resist polymer (P) comprising a structural unit of
The structural unit having the polar group is at least one member selected from the group consisting of a structural unit having a lactone skeleton, or —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a methoxy group, a carboxy group, and an amino group. A structural unit having a hydrophilic group;
The structural unit having an acid-eliminable group has an alicyclic hydrocarbon group having 6 to 20 carbon atoms and is tertiary at a binding site with an oxygen atom constituting an ester bond of (meth) acrylic acid ester. A (meth) acrylic acid ester having a carbon atom or an alicyclic hydrocarbon group having 6 to 20 carbon atoms and a -COOR group (R has a substituent) A tertiary hydrocarbon group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxepanyl group) is a structural unit derived from a (meth) acrylic ester bonded directly or via a linking group. ,
A ratio X _Ui (mol%) of each structural unit (Ui) (where i is an integer of 1 to n) in the polymer (P) and contained in the polymer (P) by size exclusion chromatography. A polymer (PH) having a molecular weight equal to or higher than the weight average molecular weight (Mw) is fractionated into m fractions (where m is an integer of 4 or more), and the polymer contained in each fraction fractionated ( PHj) (where j is an integer from 1 to m), and the ratio X _Uij (mol%) of each structural unit (Ui) satisfies the following formula (1) and is a resist made of a resist polymer. material.
0.95 ≦ X _Uij / X _Ui ≦ 1.05 (1).   A resist composition comprising the resist material according to claim 1. Applying the resist composition according to claim 2 on a substrate to be processed to form a resist film;
Irradiating the resist film with light having a wavelength of 250 nm or less to form a latent image;
And a step of developing the resist film on which the latent image is formed with a developer.

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