JP2017043741A - Polymer having thiol group at molecular end, method of producing that polymer, polymer having carbon-carbon double bond at molecular end, and pattern formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which can more faithfully transfer a pattern based on a microphase-separated structure on a parent substrate onto another substrate in MTP (Molecular Transfer Printing).SOLUTION: A polymer has a structure represented by the general formula (1) in the figure. (In the formula, the symbol * represents a binding site to another atom; Brepresents a polymer block comprising a structural unit derived from (meth)acrylic acid ester; and W represents a C2-61 divalent hydrocarbon group that may include nitrogen atoms, oxygen atoms and sulfur atoms at any positions.)SELECTED DRAWING: Figure 4

Description

  The present invention relates to a polymer used as a polymer ink used in self-assembled (DSA) lithography, a method for producing the polymer, an intermediate, and a pattern forming method using the polymer.

  With miniaturization of various electronic device structures such as semiconductor devices, pattern miniaturization in a lithography process is required. At present, it is possible to form a fine pattern having a line width of about 30 nm using ArF excimer laser light or the like, but a finer pattern has been demanded.

  Examples of a finer pattern forming method include X-rays, electron beams, and ultrashort ultraviolet (EUV) photolithography using a light source having a shorter wavelength than ArF excimer laser light. However, these technologies have problems such as light source output and increased semiconductor device manufacturing costs.

  On the other hand, as one of new pattern forming methods, several methods using a phase separation structure by so-called self-assembly (DSA) that spontaneously forms an ordered pattern have been proposed. Self-organization refers to a phenomenon in which an organization or structure is spontaneously constructed without being caused solely by control from external factors. For example, a method of forming an ultrafine pattern by self-assembly using a block copolymer obtained by copolymerizing a monomer compound having one property and a monomer compound having a different property is known (patent) Reference 1). According to this method, by annealing the composition containing the block copolymer, a pattern can be formed in a self-aligned manner utilizing microphase separation in which polymer structures having the same properties are gathered together.

  In order to form a pattern by DSA lithography, it is necessary to previously form a pre-pattern that serves as a guide on the substrate. Although the pre-pattern is roughly classified into a physical guide and a chemical guide, both of them need to go through a normal photolithography process, and thus still have a problem from the viewpoint of manufacturing cost.

  As a cost improvement measure in DSA lithography, a method called MTP (Molecular Transfer Printing) has been proposed (see Patent Document 2). In this method, first, a block copolymer that self-assembles with one or more types of polymers (polymer ink) having a functional group such as a hydroxyl group at a terminal site on a base substrate on which a pre-pattern (physical guide or chemical guide) is formed. And a self-assembled film is formed by annealing. At this time, the high-polarity polymer ink is unevenly distributed near the high-polarity portion of the self-assembled film, and the low-polarity polymer ink is unevenly distributed near the low-polarity portion of the self-assembled film. After another substrate is brought into contact with the formed self-assembled film, when the other substrate is peeled off from the base substrate, a part of the polymer ink moves onto the other substrate, and the microphase on the base substrate is moved. A pattern based on the separation structure is transferred. The transferred pattern becomes a pre-pattern (chemical guide) on the other substrate, and DSA lithography can be performed on the other substrate.

  According to this method, it is possible to reuse the base substrate by performing an appropriate process after the transfer, and it is also possible to transfer the phase separation structure to another substrate based on the substrate after the transfer. . That is, the photolithography process is required only at the time of forming a pre-pattern for the first production of the base substrate, and thereafter, the pattern can be formed one after another without performing the photolithography process.

  The polymer ink conventionally used in MTP is a polymer having a hydroxyl group at the terminal site, but it cannot be said that the substrate adhesion of this polymer ink is still sufficient, and there are defects in the pattern after transfer, There were problems such as an increase in Width Roughness (LWR).

JP 2008-149447 A US Patent Application Publication No. 2009/0260750

  An object of the present invention is to provide a polymer capable of more faithfully transferring a pattern based on a microphase-separated structure on a base substrate to another substrate in MTP, a method for producing the polymer, an intermediate, and pattern formation using the polymer It is to provide a method.

  As a result of intensive studies, the present inventors have, as a terminal block, a polymer block composed of a structural unit derived from (meth) acrylic acid ester, and a polymer in which a thiol group (SH group) is introduced at the terminal of the terminal block As a polymer ink, the inventors have found that a pattern based on a microphase separation structure on a base substrate can be more faithfully transferred onto another substrate, and the present invention has been completed.

That is, the present invention provides the following [1] to [9].
[1] A polymer having a structure represented by the following general formula (1).

(In the formula, * represents a bond with another atom, B ³ represents a polymer block composed of a structural unit derived from (meth) acrylic acid ester, W represents a nitrogen atom, an oxygen atom and an arbitrary position) Represents a C2-61 divalent hydrocarbon group which may contain a sulfur atom.)
[2] The polymer of [1] represented by the following general formula (2).

(In the formula, B ³ and W are as defined above, and B ¹ is a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester). B ² represents a polymer block composed of a structural unit derived from a conjugated diene or a structural unit derived from a diphenylethylene derivative, and m and n each independently represents 0 or 1.)
[3] The polymer according to [2], wherein m and n are 0.
[4] The polymer according to any one of [1] to [3], wherein B ³ is a polymer block synthesized by an anionic polymerization method comprising a structural unit derived from a (meth) acrylic acid ester.
[5] The polymer according to any one of [1] to [4], wherein W is represented by the following general formula (3).

(In the formula, ** represents a bond to B ³ , *** represents a bond to SH, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen atom. Alternatively, it represents a hydroxyl group, and W ¹ represents a C 1-50 divalent hydrocarbon group or a single bond that may contain a nitrogen atom, an oxygen atom and a sulfur atom at any position.
[6] The following general formula (4)

(In the formula, B ^{1 to} B ³ , R ¹ , X, m, and n are as defined above, R ^{2 to} R ⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and W ² represents Represents a hydrocarbon group having 1 to 9 carbon atoms or a single bond which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position, and R ² and R ³ may be bonded to each other to form a cyclic structure; .)
A polymer represented by the following general formula (5)

(In the formula, R ⁵ represents a hydrocarbon group having 1 to 10 carbon atoms.)
Is reacted with the thiocarboxylic acid represented by the following general formula (6):

(In the formula, B ^{1 to} B ³ , R ^{1 to} R ⁵ , X, W ² , m, and n are as defined above.)
The method for producing a polymer according to [5], comprising synthesizing the polymer represented by formula (1) and treating the polymer under acidic or basic conditions.
[7] The following general formula (4)

(In the formula, B ^{1 to} B ³ , R ^{1 to} R ⁴ , X, W ² , m, and n are as defined above.)
And a polymer represented by the following general formula (7)

(W ⁴ represents a C 1-9 divalent hydrocarbon group which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position.)
The method for producing a polymer according to [5], wherein the dithiol represented by formula (5) is reacted.
[8] A polymer represented by the following general formula (4).

(In the formula, B ^{1 to} B ³ , R ^{1 to} R ⁴ , X, W ² , m, and n are as defined above.)
[9] Step 1 for producing a base substrate having a pre-pattern;
Step 2 of forming a self-assembled film on the base substrate using a composition comprising a block copolymer that performs self-assembly and a polymer of any one of [1] to [5];
After bringing the surface of another substrate into contact with the surface of the self-assembled film formed on the base substrate, the other substrate is peeled off, and a part of the polymer of the present invention is placed on the surface of the other substrate. Moving step 3;
Applying a self-assembled composition containing a block copolymer on the surface of the other substrate to form a self-assembled film;
And 5 for removing a part of the phase of the self-assembled film;
A pattern forming method including:

  By using the polymer of the present invention as a polymer ink in MTP, a pattern based on a microphase separation structure on a base substrate can be transferred onto another substrate more faithfully.

In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state after forming the pre-pattern 12 (chemical guide) on the board | substrate 11. FIG. In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state after forming the mixed polymer film | membrane 13 containing the polymer of this invention on the pre-pattern 12 (chemical guide). In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state after changing the mixed polymer film 13 into the self-organization film | membrane 14 by annealing. In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state which made the surface of another board | substrate 15 contact the surface of the self-organization film | membrane 14. FIG. In the pattern forming method of the present invention, a pre-pattern 16 (chemical guide) is formed on the surface of the substrate 15 by moving a part of the polymer of the present invention present in the self-assembled film 14 on the surface of the substrate 15. It is a schematic diagram which shows an example of the state after letting it be made. In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state after forming the self-organization film | membrane 17 (17a + 17b) on the pre-pattern 16. FIG. In the pattern formation method of this invention, it is a schematic diagram which shows an example of the state after removing the one part phase 17b of the self-organization film | membrane 17. FIG.

[Polymer of the present invention]
The polymer of the present invention has a structure represented by the following general formula (1).

(In the formula, * represents a bond with another atom, B ³ represents a polymer block composed of a structural unit derived from (meth) acrylic acid ester, W represents a nitrogen atom, an oxygen atom and an arbitrary position) Represents a C2-61 divalent hydrocarbon group which may contain a sulfur atom.)

  In the general formula (1), * represents a bond with another atom. The “other atom” may be, for example, an atom constituting a group derived from a polymerization initiator or an atom constituting another polymer block, and is not limited thereto. .

The polymer of the present invention has a polymer block composed of a structural unit derived from (meth) acrylic acid ester as an end block, and an SH group is introduced at the end of the end block, that is, the general formula (1 ) Structure is important, and other parts can be freely designed.
For example, when the structure of the general formula (1) itself is used as a polymer as it is or combined with an arbitrary polymer block having a high polarity, when used as a polymer ink, Affinity increases.
Further, by combining the structure of the general formula (1) with an arbitrary polymer block having a low polarity, the affinity with a low polarity portion in the self-assembled composition is increased when used as a polymer ink.

  Examples of the polymer of the present invention include those represented by the following general formula (2) (hereinafter referred to as polymer (2)).

(Wherein B ³ and W are as defined above. B ¹ is a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester). B ² represents a polymer block composed of a structural unit derived from a conjugated diene or a structural unit derived from a diphenylethylene derivative, and m and n each independently represents 0 or 1.)

Examples of the vinyl aromatic compound constituting B ¹ include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-tert-butyl styrene, 2,4-dimethyl. Styrene compounds such as styrene, 2,4,6-trimethylstyrene, p-methoxystyrene, p-tert-butoxystyrene; vinylnaphthalene compounds such as 1-vinylnaphthalene and 2-vinylnaphthalene; 2-vinylanthracene, 9 -Vinylanthracene compounds such as vinylanthracene. B ¹ may be composed of one kind of these vinyl aromatic compounds, or may be composed of two or more kinds in combination.
Among the vinyl aromatic compounds, it is preferably composed of styrene, α-methylstyrene, p-tert-butylstyrene, and more preferably composed of only styrene or only p-tert-butylstyrene. .

In this specification, “(meth) acrylic acid ester” refers to methacrylic acid ester or acrylic acid ester.
Examples of (meth) acrylic acid ester constituting B ¹ include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate. Methacrylic acid alkyl esters such as cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate And alkyl acrylate esters such as tert-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.
Among them, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, n-acrylate Propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, and tert-butyl acrylate are preferred.
B ¹ may be composed of one type of these (meth) acrylic acid alkyl esters, or may be composed of two or more types in combination.

The number average molecular weight of B ¹ is preferably 200 to 30000, more preferably 500 to 20000, and still more preferably 1000 to 10,000.

Examples of the conjugated diene constituting B ² include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and the like. Among these, butadiene, isoprene or 2,3-dimethyl-1,3-butadiene is preferable. B ² may be composed of one or more of these conjugated dienes, but is preferably composed of one kind alone.

When B ² is a polymer block composed of a structural unit derived from a conjugated diene, the number average molecular weight is preferably 50 to 3000, more preferably 50 to 2000, and more preferably 50 to 1000. Further preferred. By setting the number average molecular weight within the above range, a sufficiently fine and satisfactory pattern can be formed.

B ² may be a structural unit derived from a diphenylethylene derivative. In the present invention, the diphenylethylene derivative refers to a compound in which two of the hydrogen atoms of ethylene are substituted with a phenyl group. Examples of the diphenylethylene derivative include 1,1-diphenylethylene, trans-1,2-diphenylethylene, cis-1,2-diphenylethylene, and the like. Among these, 1,1-diphenylethylene is preferable.

Examples of the (meth) acrylic acid ester constituting B ³ include those described above as the (meth) acrylic acid ester constituting B ¹ , and preferred ones are also the same.
B ³ may be composed of one kind of these (meth) acrylic acid alkyl esters, or may be composed of two or more kinds in combination.
The number average molecular weight of B ³ is preferably 200 to 30000, more preferably 500 to 20000, and still more preferably 1000 to 10,000.

In the general formula (2), n represents 0 or 1.
(1) When n is 0, the polymer of the present invention is added to a homopolymer of (meth) acrylate ester or a copolymer of plural types of (meth) acrylate ester via W which is a linker (bonding group). An SH group is introduced. In this case, the polymer of the present invention generally has a high polarity, and when used as a polymer ink, there is a tendency that the affinity with the high polarity portion in the self-assembled composition is increased.
(2) When n is 1 and B ¹ is a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, the same effect as the above (1) can be expected.
(3) When n is 1 and B ¹ is a polymer block composed of a structural unit derived from a vinyl aromatic compound, the polymer of the present invention has a structure having both a low-polar part and a high-polar part. ^{Depending on} the number average molecular weight and polarity of ¹ , when the contribution of the low polarity portion is large, the affinity with the low polarity portion in the self-assembled composition tends to be high when used as a polymer ink.

In the general formula (2), m represents 0 or 1.
From the viewpoint of ease of production of the polymer (2), when n is 1 and B ¹ is a polymer block composed of a structural unit derived from a vinyl aromatic compound, m is preferably 1.

W represents a C2-61 divalent hydrocarbon group which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position. W is usually a linker (bonding group) moiety that is introduced when SH is introduced into the terminal of B ³ , and its structure is basically not limited. Especially, it is preferable that the nitrogen atom, oxygen atom, and sulfur atom contained in W are 0 to 6 in total, more preferably 0 to 5 in total, and further more preferably 0 to 4 in total. In particular, it is preferable that W does not contain a nitrogen atom and contains 0 to 4 oxygen atoms or sulfur atoms in total. Further, when W contains a nitrogen atom, an oxygen atom and a sulfur atom, it is preferable that these atoms are not adjacent to each other. W preferably has 2 to 41 carbon atoms, more preferably 2 to 33 carbon atoms, still more preferably 2 to 25 carbon atoms, and most preferably 2 to 21 carbon atoms.

  From the viewpoint of ease of production, W preferably has a structure represented by the following general formula (3).

(In the formula, ** represents a bond to B ³ , *** represents a bond to SH, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen atom. Alternatively, it represents a hydroxyl group, and W ¹ represents a C 1-50 divalent hydrocarbon group or a single bond that may contain a nitrogen atom, an oxygen atom and a sulfur atom at any position.

The hydrogen atom or hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, A hydrogen atom or a methyl group is more preferable, and a hydrogen atom is most preferable.

W ¹ represents a C 1-50 divalent hydrocarbon group or a single bond which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position. Among them, the total number of nitrogen atoms, oxygen atoms, and sulfur atoms contained in W ¹ is preferably 0 to 5, more preferably 0 to 4, and even more preferably 0 to 3 in total. . In particular, W ¹ preferably does not contain a nitrogen atom and contains 0 to 3 oxygen atoms and sulfur atoms in total. Further, the nitrogen atom in W ^1, if it contains an oxygen atom and a sulfur atom, these atoms are preferably not adjacent. The carbon number of W ¹ is preferably ¹ to 35, more preferably 1 to 29, still more preferably 1 to 23, and most preferably 1 to 20.

[Method for producing polymer of the present invention]
The method for producing the polymer of the present invention is not particularly limited, and the polymer can be produced by combining known reactions and reactions based thereon.
For example, the polymer (2) can be produced by the following production method 1 or production method 2.

(Production method 1)
The production method 1 has the following general formula (4)

(In the formula, B ^{1 to} B ³ , R ¹ , X, m, and n are as defined above. R ^{2 to} R ⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and W ² represents A divalent hydrocarbon group having 1 to 9 carbon atoms which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position, or a single bond, R ² and R ³ are bonded to each other to form a cyclic structure. May be.)
And a polymer represented by the following general formula (5):

(Wherein R ⁵ represents a hydrocarbon group having 1 to 10 carbon atoms)
Is reacted with a thiocarboxylic acid represented by the following formula (hereinafter referred to as thiocarboxylic acid (5)) to give the following general formula (6)

(In the formula, B ^{1 to} B ³ , R ^{1 to} R ⁵ , X, W ² , m, and n are as defined above.)
Is synthesized (hereinafter referred to as polymer (6)), and the polymer is treated under acidic or basic conditions to produce polymer (2).

Examples of the hydrogen atom represented by R ^{2 to} R ⁵ or the hydrocarbon group having 1 to 10 carbon atoms include the same ones as R ^1, and preferred ones are also the same.

W ² represents a C 1-9 divalent hydrocarbon group or a single bond which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position. Of these, the nitrogen atom contained in W ^2, it is preferred that the oxygen atom and a sulfur atom is the sum 0-2, more preferably the sum is 0-1, and more preferably does not contain. Further, the nitrogen atom in W ^2, if it contains an oxygen atom and a sulfur atom, these atoms are preferably not adjacent.
Examples of W ² include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a 1,4-cyclohexylene group, and a 1,4-phenylene group. Among these, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a nonylene group are preferable, and a pentylene group, a hexylene group, a heptylene group, and an octylene group are more preferable.

  The method for obtaining the polymer (4) will be described later. As the thiocarboxylic acid (5), a commercially available product may be used, or it may be produced by a known method.

  The solvent used in the reaction of the polymer (4) and the thiocarboxylic acid (5) is not particularly limited as long as the reaction is not inhibited. For example, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; chlorobenzene, fluoro Halogenated aromatic hydrocarbons such as benzene; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1, 2 -Ethers such as dimethoxyethane, diglyme, triglyme and tetraglyme; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; acetonitrile and the like. These may be used alone or in combination of two or more. The amount of the solvent used is preferably 100 parts by mass or less and more preferably 10 parts by mass or less with respect to 1 part by mass of the polymer (4) from the viewpoint of reaction rate and amount of waste solvent.

  The reaction temperature in the reaction between the polymer (4) and the thiocarboxylic acid (5) is preferably in the range of −50 to 200 ° C., and more preferably in the range of 0 to 100 ° C.

In the reaction of the polymer (4) and the thiocarboxylic acid (5), a radical initiator may be added as necessary. Examples of the radical initiator include azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, Examples thereof include peroxides such as dicumyl peroxide and acetyl peroxide. Among these, azobisisobutyronitrile is preferable from the viewpoint of availability.
The amount of the radical initiator used is preferably in the range of 0.2 to 3.0 mol with respect to 1 mol of the polymer (4). From the viewpoint of economy and ease of post-treatment, 0.2 to The range of 1.0 mol is more preferable.

  For example, polymer (6) can be obtained by dissolving polymer (4) and thiocarboxylic acid (5) in a solvent and stirring.

  The polymer (2) can be obtained by treating the polymer (6) under acidic or basic conditions.

  The solvent used in the treatment under acidic or basic conditions is not particularly limited as long as the reaction is not inhibited. For example, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; chlorobenzene, fluorobenzene, etc. Halogenated aromatic hydrocarbons; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane , Ethers such as diglyme, triglyme and tetraglyme; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; acetonitrile and the like. These may be used alone or in combination of two or more. The amount of the solvent used is preferably 100 parts by mass or less and more preferably 10 parts by mass or less with respect to 1 part by mass of the polymer (6) from the viewpoint of the reaction rate and the amount of the waste solvent.

  The reaction temperature in the treatment under acidic or basic conditions is preferably in the range of −50 to 200 ° C., and more preferably in the range of 0 to 100 ° C.

  Examples of additives used when the treatment is carried out under acidic conditions include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; acetic acid, propionic acid, oxalic acid, p-toluenesulfonic acid monohydrate, trifluoromethanesulfonic acid And organic acids such as Of these, p-toluenesulfonic acid monohydrate and trifluoromethanesulfonic acid are preferable.

  Examples of the additive used when the treatment is performed under basic conditions include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium- Examples thereof include tert-butoxide. Of these, sodium methoxide is preferred.

  The amount of the acidic or basic additive used is preferably in the range of 0.2 to 3.0 mol with respect to 1 mol of the polymer (6). From the viewpoint of economy and ease of post-treatment, A range of 0.2 to 1.2 mol is more preferable.

  For example, polymer (2) can be obtained by dissolving polymer (6) in a solvent, then adding sodium methoxide and stirring.

(Manufacturing method 2)
Production method 2 comprises polymer (4) and the following general formula (7)

(W ⁴ represents a C 1-9 divalent hydrocarbon group which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position.)
Is a method for producing a polymer (2) by reacting with dithiol (hereinafter referred to as dithiol (7)).

W ⁴ represents a C 1-9 divalent hydrocarbon group which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position. Of these, the nitrogen atom contained in the W ^4, it is preferable oxygen atom and a sulfur atom is the sum 0-2. Further, the nitrogen atom in W ^4, if it contains an oxygen atom and a sulfur atom, these atoms are preferably not adjacent. Examples of W ⁴ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1-methyloctylene group, 1-isopropyloctylene group, 1- tert-butyloctylene group, 1-phenyloctylene group, 1,4-cyclohexylene group, 1,4-phenylene group, 2-oxooctylene group, 2-thiaoctylene group, 2-azaoctylene group, 2-aza-2-ene Examples include a methyloctylene group, a 3,6-dioxaoctylene group, a 2-aza-4-oxaoctylene group, and a 2-oxa-4-thiaoctylene group. Among these, 3,6-dioxaoctylene group is preferable from the viewpoint of easy availability of raw materials.

  The solvent used in the above reaction is not particularly limited as long as the reaction is not inhibited. For example, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene; Diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme and other ethers; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated hydrocarbons; acetonitrile and the like It is done. These may be used alone or in combination of two or more. It is preferable that the usage-amount of a solvent is 100 mass parts or less with respect to 1 mass part of polymers (4) from the point of reaction rate or a waste solvent amount.

  The reaction temperature of the above reaction is desirably in the range of −50 to 200 ° C., and more preferably in the range of 0 to 100 ° C.

  In the above reaction, a radical initiator may be added as necessary. Examples of the radical initiator include azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, Examples thereof include peroxides such as dicumyl peroxide and acetyl peroxide. Among these, azobisisobutyronitrile is preferable from the viewpoint of availability.

  The amount of the radical initiator used is preferably in the range of 0.2 to 3.0 mol with respect to 1 mol of the polymer (4). From the viewpoint of economy and ease of post-treatment, 0.2 to The range of 1.0 mol is more preferable.

  For example, the polymer (4) can be obtained by dissolving the polymer (4) in a solvent, then adding azobisisobutyronitrile and dithiol (7) and stirring.

[Production Method of Polymer (4)]
The polymer (4) used in production method 1 or 2 can be produced by the following procedure.

(Manufacture of block copolymers, etc.)
First, a structure represented by the following general formula (hereinafter referred to as a block portion) is manufactured by the following procedure.

(Wherein B ^{1 to} B ³ are as defined above.)

In accordance with a known anionic polymerization method, a predetermined monomer polymerization reaction is performed stepwise, that is, an anionic polymerization of an aromatic vinyl compound, a conjugated diene, a diphenylethylene derivative or a (meth) acrylic acid ester in a desired order. It can manufacture by carrying out in steps. Each monomer to be used is preferably sufficiently dried in advance under an inert gas atmosphere such as nitrogen, argon or helium from the viewpoint of allowing the polymerization reaction to proceed smoothly. In the drying treatment, a dehydrating agent or a desiccant such as calcium hydride, molecular sieves or activated alumina is preferably used.

  The anionic polymerization reaction conditions can be appropriately selected from the range of polymerization temperature −100 ° C. to + 100 ° C. and polymerization time 1 to 100 hours. The anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium.

  As a polymerization initiator in anionic polymerization, a known anionic polymerization initiator can be used, and examples thereof include alkali metals such as metallic sodium and metallic lithium; organic lithium compounds, organic sodium compounds, organic potassium compounds, and organic magnesium compounds. It is done.

  Examples of the organic lithium compound include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, isobutyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, Alkyllithium and alkyldilithium such as tetramethylenedilithium, pentamethylenedilithium and hexamethylenedilithium; aryllithium and aryldilithium such as phenyllithium, m-tolyllithium, p-tolyllithium, xylyllithium and lithium naphthalene Benzyl lithium, diphenylmethyl lithium, trityl lithium, 1,1-diphenyl-3-methylpentyl lithium, α-methylstyryl lithium, diisopropeni Aralkyllithium and aralkyldilithium such as dilithium produced by the reaction of benzene and butyllithium; lithium amides such as lithium dimethylamide, lithium diethylamide and lithium diisopropylamide; lithium methoxide, lithium ethoxide, lithium n-propoxide, lithium isoform Lithium alkoxides such as propoxide, lithium n-butoxide, lithium sec-butoxide, lithium tert-butoxide, lithium pentyl oxide, lithium hexyl oxide, lithium heptyl oxide, lithium octyl oxide; lithium phenoxide, lithium 4-methylphenoxide, lithium benzyl oxide And lithium 4-methylbenzyl oxide.

  Examples of the organic sodium compound and the organic potassium compound include those obtained by replacing lithium in the organic lithium compound with sodium or potassium.

  Examples of the organic magnesium compound include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, ethyl butyl magnesium, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, tert-butyl magnesium chloride, tert-butyl. Examples thereof include magnesium bromide.

  Among these polymerization initiators, an organic lithium compound is preferable from the viewpoint of safety, handleability, high polymerization initiation efficiency, and smooth anion polymerization reaction. Among them, n-butyllithium, sec-butyllithium, tert-butyl are preferable. Particularly preferred are lithium, diphenylmethyllithium, 1,1-diphenyl-3-methylpentyllithium, and α-methylstyryllithium. As the polymerization initiator, one of the above polymerization initiators may be used alone, or two or more thereof may be used in combination.

  The amount of the polymerization initiator used is not particularly limited, but is usually in the range of 0.1 to 100 mmol / l as the concentration in the polymerization reaction solution, and preferably in the range of 1 to 20 mmol / l. This is preferable because it can be manufactured smoothly.

The anionic polymerization is preferably performed in the presence of a solvent. The solvent to be used is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. For example, aliphatic hydrocarbons such as pentane, n-hexane, and octane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene; and ethers such as diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole and diphenyl ether. Among these, cyclohexane, toluene, and xylene are preferably used from the viewpoints of high solubility of the generated block portion, difficulty in mixing with wastewater, and easy recovery and purification of the solvent. These solvents may be used alone or in combination of two or more. In addition, it is preferable from the point which advances the anionic polymerization reaction that the solvent to be used refine | purifies previously by deaerating and dehydrating.
Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, 1-100 mass parts is preferable with respect to 1 mass part of total amounts of the monomer used for anionic polymerization.

In the above anionic polymerization, organic aluminum is formed from the viewpoint of forming B ³ , that is, from the viewpoint of making the polymerization conditions milder and polymerizing results (living property, block efficiency, etc.) when polymerizing the above-mentioned (meth) acrylic acid ester. It is extremely possible to carry out an anionic polymerization reaction by further coexisting a compound, preferably a tertiary organoaluminum compound having a chemical structure represented by the formula Al—O—Ar (wherein Ar represents an aromatic ring) in the molecule. It is preferable (for example, refer to JP 2001-158805 A).

  As the tertiary organoaluminum compound having a chemical structure represented by the above formula Al-O-Ar (wherein Ar represents an aromatic ring) in the molecule, for example, ethyl bis (2,6-ditert-butyl-4- Methylphenoxy) aluminum, ethylbis (2,6-ditert-butylphenoxy) aluminum, ethyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di) tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-ditert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, n -Octylbis (2,6-ditert-butyl-4-methylphenoxy Aluminum, n-octylbis (2,6-ditert-butylphenoxy) aluminum, n-octyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, methoxybis (2,6-di) tert-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-ditert-butylphenoxy) aluminum, methoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, ethoxybis ( 2,6-ditert-butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-ditert-butylphenoxy) aluminum, ethoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy) ] Aluminum, isop Poxybis (2,6-ditert-butyl-4-methylphenoxy) aluminum, isopropoxybis (2,6-ditert-butylphenoxy) aluminum, isopropoxy [2,2′-methylenebis (4-methyl-6- tert-butylphenoxy)] aluminum, tert-butoxybis (2,6-ditert-butyl-4-methylphenoxy) aluminum, tert-butoxybis (2,6-ditert-butylphenoxy) aluminum, tert-butoxy [2, 2'-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, tris (2,6-ditert-butyl-4-methylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum and the like. It is done. Among them, isobutylbis (2,6-ditert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-ditert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6) -Tert-Butylphenoxy)] aluminum is particularly preferred from the viewpoints of high living property, availability, ease of handling, and the like. These may be used alone or in combination of two or more.

The amount of the organoaluminum compound used can be appropriately selected according to the type of solvent used when forming B ³ by anionic polymerization and various polymerization conditions. Usually, it is preferable to use an organoaluminum compound in an equimolar ratio or more with respect to an alkali metal atom (or anion center) such as lithium, sodium or potassium in the polymerization initiator to be used. It is more preferable to use in the ratio.

When an anionic polymerization reaction is carried out by further coexisting the organoaluminum compound when forming B ³ , the block efficiency and the polymerization rate in anionic polymerization of (meth) acrylic acid ester are improved, and further, the deactivation is suppressed to reduce the living property. As long as the polymerization reaction is not adversely affected, ether compounds in the system; tertiary polyamines; inorganic salts such as lithium chloride; metal alkoxide compounds such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethyl Additives such as organic quaternary salts such as ammonium chloride and tetraethylphosphonium bromide may coexist, and it is particularly preferable to coexist an ether compound or a tertiary polyamine compound.

  The ether compound can be appropriately selected from compounds having an ether bond (—O—) in the molecule and containing no metal component, such as 12-crown-4, 15-crown-5, 18-crown. Cyclic ethers having two or more ether bonds in the molecule, such as crown ethers such as -6; acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, anisole; 1,2-dimethoxyethane, 1 , 2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2 -Diisopropoxypropane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3 Dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane Acyclic diether such as 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene Acyclic triethers such as glycol diethyl ether and dibutylene glycol diethyl ether; triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether Ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, tetrabutylene glycol And acyclic ethers having one or more ether bonds in the molecule, such as dialkyl ethers of polyalkylene glycols such as diethyl ether. Among these, acyclic ether is preferable, and diethyl ether, 1,2-dimethoxyethane, and triethylene glycol dimethyl ether are more preferable.

  The tertiary polyamine compound can be appropriately selected from compounds having two or more tertiary amine structures in the molecule. In this specification, “tertiary amine structure” means a partial chemical structure in which three carbon atoms are bonded to one nitrogen atom, and the nitrogen atom is bonded to three carbon atoms. As long as it is, it may constitute a part of the aromatic ring. Examples of tertiary polyamine compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyl. Linear polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexahydro-1, 3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16 A non-aromatic heterocyclic compound such as hexaazacyclooctadecane; an aromatic heterocyclic compound such as 2,2′-bipyridyl, 2,2 ′: 6 ′, 2 ″ -terpyridine; Etc., and the like.

  When the above ether compound or tertiary polyamine compound is allowed to coexist, the amount is not particularly limited, but the total number of moles of the ether compound and tertiary polyamine compound is such as lithium, sodium, potassium, etc. in the polymerization initiator used. It is usually preferably 0.1 times or more, more preferably 0.3 times or more, and further preferably 0.5 times or more with respect to the number of moles of alkali metal atoms (or anion centers). . Moreover, it is preferable that the total amount of an ether compound and a tertiary polyamine compound is about 80 mass% or less with respect to a polymerization system.

(Introduction of carbon-carbon double bond)
After the above anionic polymerization reaction, the polymer (4) can be produced by reacting the compound having a carbon-carbon double bond with the growth terminal of the block copolymer.

  Examples of the compound having a carbon-carbon double bond that gives a polymer (4) in which X is a hydrogen atom include 5-chloro-1-pentene, 5-bromo-1-pentene, 6-chloro-1-hexene, and 6-bromo-. 1-hexene, 7-chloro-1-heptene, 7-bromo-1-heptene, 8-chloro-1-octene, 8-bromo-1-octene, 8-bromo-8-methyl-1-octene, 8-bromo-8-isopropyl- 1-octene, 8-bromo-8-tert-butyl-1-octene, 8-bromo-8-cyclohexyl-1-octene, 8-bromo-8-phenyl-1-octene, 8-bromo-2-methyl-1-octene, 8-bromo-1-methyl-1-octene, 8-bromo-2-methyl-2-nonene, 8-bromo-1,2-dimethyl-2-none Etc. The. Of these, 5-bromo-1-pentene and 6-bromo-1-hexene are preferable from the viewpoints of availability of raw materials and ease of synthesis.

  Examples of the compound having a carbon-carbon double bond that gives the polymer (4) in which X is a hydroxyl group include 4-pentenylaldehyde, 5-hexenylaldehyde, 6-heptenylaldehyde, 7-octenylaldehyde, and 7-methyl. -7-octenyl aldehyde, 7-isopropyl-7-octenyl aldehyde, 7-tert-butyl-7-octenyl aldehyde, 7-cyclohexyl-7-octenyl aldehyde, 7-phenyl-7-octenyl aldehyde, 7 -Nonenyl aldehyde, 7-methyl-7-nonenyl aldehyde, 7,8-dimethyl-7-nonenyl aldehyde, (7-octenyl) methyl ketone, isopropyl (7-octenyl) ketone, cyclohexyl (7-octenyl) ketone, Phenyl (7-octenyl) ketone, (7-methyl 7-octenyl) methylketone, (7-isopropyl-7-octenyl) methylketone, (7-tert-butyl-7-octenyl) methylketone, (7-cyclohexyl-7-octenyl) methylketone, (7-phenyl-7-octenyl) Examples thereof include methyl ketone, (7-nonenyl) methyl ketone, (7-methyl-7-nonenyl) methyl ketone, (7,8-dimethyl-7-nonenyl) methyl ketone and the like. Among these, 4-pentenyl aldehyde, 5-hexenyl aldehyde, 6-heptenyl aldehyde, and 7-octenyl aldehyde are preferable from the viewpoint of ease of synthesis and availability of raw materials.

The amount of the compound having a carbon-carbon double bond used is preferably in the range of 0.5 mol to 50 mol with respect to 1 mol of the growth terminal of the block copolymer, from the viewpoint of economy and ease of post-treatment. Is more preferably in the range of 1 mol to 20 mol.
The reaction time when introducing the carbon-carbon double bond is preferably in the range of 1 minute to 10 hours, and more preferably in the range of 1 minute to 3 hours from the viewpoint of economy. The reaction temperature is preferably in the range of −100 ° C. to + 100 ° C., and more preferably in the range of −100 ° C. to 50 ° C. from the viewpoint of the stability of the growth end.

After the above-mentioned anionic polymerization reaction, for example, methanol, acetic acid, hydrochloric acid in methanol or the like as a polymerization terminator, usually, preferably an alkali metal atom (or anion center) such as lithium, sodium or potassium in the polymerization initiator used. The polymerization reaction is stopped by adding to the reaction mixture in the range of 1 to 100 moles.
The method of isolating the polymer (4) from the reaction mixture is, for example, a method of pouring the reaction mixture into a poor solvent of the polymer (4) to precipitate, or removing the solvent (4) from the reaction mixture to remove the polymer (4). The acquisition method etc. are mentioned.

[Isolation / Purification of Polymer of the Present Invention]
The polymer of the present invention produced by the above method is, for example, a method of pouring the reaction mixture into a poor solvent of the polymer of the present invention to precipitate, a method of obtaining the polymer of the present invention by distilling off the solvent from the reaction mixture, etc. Can be isolated.

  If the polymer component of the present invention isolated from the reaction mixture contains metal components (typically lithium, sodium, potassium, aluminum, etc.) derived from the used polymerization initiator or organoaluminum compound, the present invention It is preferable to remove the metal component derived from the polymerization initiator and the organoaluminum catalyst from the polymer of the present invention as much as possible because it may adversely affect the self-assembly ability of the composition containing the polymer. As the metal removal method, for example, the polymer of the present invention is washed with an acidic aqueous solution such as hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution, tartaric acid aqueous solution, or the polymer of the present invention. Is dissolved in a solvent such as toluene, xylene, or ethyl acetate to form a solution, which is in contact with an appropriate adsorbent such as an ion exchange resin that is insoluble in the solvent and can adsorb metal components. And a method of removing them.

[Pattern formation method]
The pattern forming method of the present invention is a step 1 for producing a base substrate having a pre-pattern; a self-assembled film is formed on the base substrate using a block copolymer that performs self-assembly and a composition containing the polymer of the present invention. Step 2; contacting the surface of another substrate with the surface of the self-assembled film formed on the base substrate, then peeling the other substrate, and removing a part of the polymer of the present invention on the surface of the other substrate Step 3 for moving up; Step 4 for applying a self-assembled composition containing a block copolymer on the surface of the other substrate to form a self-assembled film; and a part of the phase of the self-assembled film Step 5 is removed. In addition, after the process 5, you may have the process 6 which etches the said board | substrate using the pattern formed at the process 5 as a mask.

(Process 1)
Step 1 is a step of manufacturing a base substrate having a pre-pattern 12 (see FIG. 1).
In this step, a physical guide formed by applying a photoresist solution on the substrate 11 and performing photolithography may be used as the pre-pattern 12. In addition, a polymer having affinity with one block of the block copolymer used in step 2 is applied to form a lower layer film, a photoresist solution is applied from above the lower layer film, and photolithography is performed. A chemical guide formed by removing or altering a part may be used as the pre-pattern 12.
By forming the pre-pattern 12, the microphase separation structure of the self-assembled film formed in the subsequent step 2 can be controlled.

As a method for forming the physical guide, a method similar to a known resist pattern forming method can be used.
For example, a resist film is formed using a commercially available chemically amplified resist composition, and then light and particle beams are irradiated onto a desired region of the resist film through a mask having a specific pattern to perform exposure. Thereafter, post exposure baking (PEB) is performed, and development is performed using a developer such as an alkali developer or an organic solvent, whereby a desired physical guide can be formed. Examples of the light and the particle beam include deep ultraviolet rays represented by ultraviolet rays, ArF excimer laser light, and KrF excimer laser light, EUV, X-rays, and charged particle beams. Of these, far ultraviolet rays and EUV are preferable. As the exposure method, immersion exposure may be used.

The polymer for forming the lower layer film used in the formation of the chemical guide can be appropriately selected according to the type of the block copolymer used in Step 2.
For example, when the block copolymer used in Step 2 is a diblock copolymer of styrene and methyl methacrylate (hereinafter referred to as PS-b-PMMA), a homopolymer of a vinyl aromatic compound having a hydroxyl group at the terminal is used. be able to. The vinyl aromatic compound can be the same as those that constitute the B ^1, it is preferable also the same. Here, the hydroxyl group has the effect of increasing the adhesion of the polymer to the substrate.
Moreover, the polymer of this invention can also be used as a polymer for forming an underlayer film. Since the polymer of the present invention has an SH group at the terminal, it exhibits higher adhesion to the substrate.
Examples of photolithography used for forming the chemical guide include a method using an electron beam, an X-ray, and EUV light as a light source.

(Process 2)
Step 2 is a matrix prepared in Step 1 using a block copolymer that performs self-assembly and a composition containing at least one polymer of the present invention (hereinafter referred to as “polymer ink-containing self-assembly composition”). This is a step of forming a self-assembled film 14 on a substrate (see FIGS. 2 and 3).

First, a polymer ink-containing self-assembled composition is applied on a base substrate, and a mixed polymer film 13 is formed on the base substrate. Thereafter, the mixed polymer film 13 changes to a self-assembled film 14 by annealing.
At this time, the polymer of the present invention is unevenly distributed in a portion having a high affinity with the polymer of the present invention in the microphase separation structure of the self-assembled film 14. For example, in the case of a microphase-separated structure divided into a high polar part and a low polar part, among the polymers of the present invention, a high polar one is in the high polar part of the self-assembled film 14 and a low polar one is a self-assembled film. Each of the 14 low-polarity portions is unevenly distributed.
The self-assembled film 14 may be formed after contacting another substrate to be transferred in step 3 to be described later.

  The method for applying the polymer ink-containing self-assembling composition on the substrate is not particularly limited, and examples thereof include a method of applying by a spin coating method.

Examples of the annealing method include a method of heating for a predetermined time using an oven, a hot plate, or the like. The temperature during annealing is usually 80 to 400 ° C, preferably 100 to 300 ° C, and more preferably 150 to 230 ° C. The annealing time is not particularly limited, but is usually 1 minute to 30 hours. Annealing is preferably performed in a vacuum.
The thickness of the self-assembled film 14 is usually 1 to 200 nm, preferably 20 to 200 nm, and more preferably 30 to 100 nm.

The block copolymer that performs self-assembly is not particularly limited as long as it is a copolymer having two or more polymer blocks that are incompatible with each other and has a microphase-separated structure under suitable thermodynamic conditions. Not. Examples of such block copolymers include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-tert-butyl styrene, 2,4-dimethyl styrene, 2 , 4,6-trimethylstyrene, p-trimethylsilylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylanthracene, 9-vinylanthracene, and other vinyl aromatic compounds, methyl methacrylate, ethyl methacrylate, methacrylic acid n-propyl, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, acrylic acid (Meth) such as ethyl oxalate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate And block copolymers with alkyl acrylates.
Further, it may have a conjugated diene block such as isoprene or butadiene, a dimethylsiloxane block, or the like.
The number of blocks of the block copolymer is not particularly limited, but among them, a diblock copolymer or a triblock copolymer is preferable, a diblock copolymer is more preferable, and PS-b-PMMA is more preferable.

  The polymer of the present invention plays a role as a polymer ink. In the case of using, for example, PS-b-PMMA as a block copolymer for forming a self-assembled film, among the polymers of the present invention, a vinyl aromatic compound having a SH group at the end of a (meth) acrylate block— (meth) acrylic Diblock copolymer of acid ester, vinyl aromatic compound having SH group at the end of (meth) acrylate block-conjugated diene- (meth) acrylate triblock copolymer, (meth) acryl having SH group at end Preference is given to acid ester homopolymers and the like.

An optional component can be added to the polymer ink-containing self-assembled composition as long as the effects of the present invention are not impaired. Examples of optional components include other polymers such as polystyrene and polymethyl methacrylate; polymethyl methacrylate having a terminal hydroxyl group (hereinafter referred to as PMMA-OH), and polystyrene having a terminal hydroxyl group (hereinafter referred to as PSt-OH). Polymer inks other than the polymer of the present invention; solvent; plasticizer; supercritical fluid; dopants such as boron, phosphorus, gallium, and arsenic.
Examples of the solvent include diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane and the like; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Glycol ethers such as glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether; methyl acetate, acetic acid Ethyl, propyl acetate, butyl acetate, pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, ethyl propionate, propionic acid Butyl, amyl propionate, methyl lactate, ethyl lactate, butyrate lactate , Amyl lactate, methyl 3-methoxypropionate, methyl acetoacetate, ethyl acetoacetate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dimethyl phthalate, diethyl phthalate, γ-butyrolactone, γ-valerolactone, diethyl carbonate Esters such as propylene carbonate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether propionate, Propylene glycol monomethyl ether acetate Glycol ether esters such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone, methyl-n-propyl ketone , Methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclo Octanone, methylcyclohexanone, 2,4-pentanedione, acetonyl Ketones such as acetone and acetophenone; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, cumene, diethylbenzene, isobutylbenzene, trimethylbenzene, diisopropylbenzene, and n-amylnaphthalene .

(Process 3)
In step 3, the surface of another substrate 15 is brought into contact with the surface of the self-assembled film 14 formed on the base substrate, and then the substrate 15 is peeled off, and the polymer of the present invention is placed on the surface of the other substrate 15. This is a step of moving (see FIGS. 4 and 5).

  As a method of bringing the self-assembled film 14 and the substrate 15 into contact with each other, a roll to roll method, a roll to substrate method, or the like can be used in addition to a method of pressing the substrates together. Even if the substrate 15 is curved, the pattern can be transferred as long as physical contact can be made.

Annealing may be performed during the contact.
Examples of the annealing method include a method of heating for a predetermined time using an oven, a hot plate, or the like. The temperature during annealing is usually 80 to 400 ° C, preferably 100 to 300 ° C, and more preferably 150 to 230 ° C. The annealing time is not particularly limited, but is usually 1 minute to 30 hours. Annealing is preferably performed in a vacuum.

A part of the polymer of the present invention moves from the surface of the self-assembled film 14 to the surface of the substrate 15 by interaction with the surface of the substrate 15. As a result, the pattern formed on the surface of the self-assembled film 14 is accurately transferred to the surface of the substrate 15. The transferred pattern serves as a pre-pattern 16 and functions as a chemical guide in step 4 to be described later.
Examples of the interaction include bonding by chemical reaction, absorption at the surface, absorption into the interior, etc. In the case of the polymer of the present invention, the reaction between the SH group and the substituent on the surface of the substrate 15 is mainly performed. It is considered an interaction.

  Examples of the method for removing the substrate 15 include a method of removing a block copolymer and unreacted polymer ink between substrates using a solvent such as chlorobenzene, a method using ultrasonic waves, a method of mechanically peeling, and the like. They may be used alone or in combination.

Depending on the peeling method, the base substrate can be reused in the transfer process. For example, in the method using a solvent, the self-assembled film 14 is dissolved and removed by washing. In this peeling method, since the substrate 11 is recovered without damaging the formed prepattern, it can be used again in the transfer process.
In addition, when a peeling method that does not dissolve the self-assembled film is employed, it can be used again in the transfer process by refilling the polymer of the present invention by a method such as applying a composition containing the polymer of the present invention to the self-assembled film. Is possible. Even in the case where the polymer of the present invention is not refilled, the self-assembled film can be used for multiple transfers unless the self-assembled film is dried.

(Process 4)
Step 4 is a step of forming a self-assembled film 17 on the surface of the substrate 15 by applying a self-assembled composition containing a block copolymer (see FIG. 6).

A composition having a block copolymer that performs self-assembly (hereinafter referred to as a “pattern-forming self-assembled composition”) is applied onto the substrate 15 on which the pre-pattern 16 is formed, and annealing is performed. Thus, the self-assembled film 17 is formed. As the block copolymer for self-assembly, the same one as described in Step 2 above can be used.
The phase separation structure formed in this step is composed of a plurality of phases, and the interface formed from these phases is usually substantially vertical, but the interface itself is not necessarily clear.

The self-assembling composition for pattern formation preferably contains a solvent such as toluene from the viewpoint of facilitating application onto the substrate 15.
The method for applying the self-assembling composition for pattern formation onto the substrate is not particularly limited, and examples thereof include a method of applying by a spin coating method.

  Examples of the annealing method include a method of heating for a predetermined time using an oven, a hot plate, or the like. The temperature during annealing is usually 80 to 400 ° C, preferably 100 to 300 ° C, and more preferably 150 to 230 ° C. The annealing time is not particularly limited, but is usually 1 minute to 30 hours. Annealing is preferably performed in a vacuum.

(Process 5)
Step 5 is a step of removing a part of the phase of the self-assembled film 17 (see FIG. 7).
When PS-b-PMMA is used as the block copolymer in step 4, the PMMA block phase 17b can be removed by etching using the difference in the etching rate of the phases separated by self-assembly. FIG. 8 shows a state after the PMMA block phase 17b in the phase separation structure is removed. In addition, you may irradiate a light beam as needed before this etching process. As the light beam, ultraviolet light of 254 nm can be used when the phase to be removed by etching is a PMMA block phase. Since the PMMA block phase is decomposed by the ultraviolet irradiation, the etching becomes easier.

As a method for removing the PMMA block phase 17b in the phase separation structure of the self-assembled film 17, for example, reactive ion etching (RIE) such as chemical dry etching or chemical wet etching; sputter etching or ion beam etching or the like. There are known methods such as physical etching. Of these, reactive ion etching (RIE) is preferable. Among them, chemical dry etching using CF ₄ , O ₂ gas, etc., and chemical wet etching (wet development) using a liquid etching solution such as an organic solvent or hydrofluoric acid are preferable. More preferred. Examples of such organic solvents include alkanes such as n-pentane, n-hexane, and n-heptane; cycloalkanes such as cyclohexane, cycloheptane, and cyclooctane; ethyl acetate, n-butyl acetate, i-butyl acetate, and methyl propionate. Saturated carboxylic acid esters of; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol Etc. In addition, these may be used individually by 1 type, or may use 2 or more types together.

(Step 6)
Step 6 is a step of etching the substrate after step 5 using the pattern formed in step 5 as a mask.
For example, when PS-b-PMMA is used as the block polymer, the lower layer film and the substrate can be patterned by etching using the pattern of the remaining styrene block phase 17a as a mask.
After the patterning on the substrate is completed, the phase used as a mask is removed from the substrate by dissolution treatment or the like, and a finally patterned substrate (pattern) can be obtained. As the etching method, the same method as in step 5 can be used, and the etching gas and the etching solution can be appropriately selected depending on the material of the lower layer film and the substrate. For example, when the substrate is made of a silicon material, a mixed gas of chlorofluorocarbon gas and SF ₄ can be used. When the substrate is a metal film, a mixed gas of BCl ₃ and Cl ₂ can be used.

  The pattern obtained by the method of the present invention is suitably used for semiconductor elements and the like, and the semiconductor elements are widely used for LEDs, solar cells and the like.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not restrict | limited at all by these Examples.

(Weight average molecular weight (M _w ) and number average molecular weight (M _n ))
_Mw and _Mn of the block polymer obtained in each Example and Comparative Example were obtained by using a GPC column (TSKgel SuperMultipore HM-N 3) manufactured by Tosoh Corporation by gel permeation chromatography (GPC). Measured according to the conditions of
Eluent: Tetrahydrofuran Flow rate: 0.35 ml / min Sample concentration: 0.1% by mass
Column temperature: 40 ° C
Detector: UV detector (measurement wavelength: 254 nm)
Standard material: monodisperse polystyrene

⁽¹ H-NMR analysis)
¹ H-NMR analysis was performed using Bruker AV400 and deuterated chloroform as a measurement solvent. The content ratio of each structural unit in each block polymer is calculated from the integral ratio of the peaks corresponding to each structural unit in the spectrum obtained by ¹ H-NMR, and the result of the GPC measurement and each structural unit by ¹ H-NMR are calculated. The number average molecular weight of each polymer block was calculated from the result of the content rate.

<Example 1>
(1) Synthesis of a styrene-butadiene-methyl methacrylate triblock copolymer (A1) having a carbon-carbon double bond at the end of a methyl methacrylate block A four-neck with an internal volume of 500 mL equipped with a stirrer and a thermometer The inside of the flask was purged with nitrogen, and 90 g of cyclohexane, 2.5 g of a cyclohexane solution of sec-butyllithium (corresponding to 3.90 mmol of sec-butyllithium), and 21.5 g (206.1 mmol) of styrene were added at 25 ° C. Stir for hours. Next, 11.0 g of a cyclohexane solution containing 2.1 g (39.0 mmol) of butadiene was added while stirring this solution, and the mixture was stirred at 25 ° C. for 1 hour. Subsequently, 90 g of toluene, 117.5 g of a toluene solution containing 30.6 g (58.5 mmol) of isobutylbis (2,6-ditert-butyl-4-methylphenoxy) aluminum, and 8.6 g of triethylene glycol dimethyl ether ( 48.2 mmol) was added separately, and a solution prepared by mixing was added and stirred at 25 ° C. for 1 hour. Then, it is cooled to 5 ° C. and toluene containing 2.0 g (19.5 mmol) of methyl methacrylate and 4.1 g (7.8 mmol) of isobutylbis (2,6-ditert-butyl-4-methylphenoxy) aluminum. A solution prepared by separately stirring 15.7 g of the solution at 25 ° C. for 1 hour was added, followed by stirring at 5 ° C. for 2 hours. Subsequently, 1.2 g (9.8 mmol) of 7-octenyl aldehyde was added and stirred at 5 ° C. for 2 hours, and 12.2 g (202.8 mmol) of acetic acid was added to terminate the polymerization. To the reaction mixture, 100 g of toluene and 100 g of 5% aqueous acetic acid solution were added, stirred at 80 ° C. for 1 hour, and allowed to stand at 80 ° C. to separate the aqueous layer. The same washing operation was further performed 4 times using 100 g of 5% aqueous acetic acid solution, and then 100 g of distilled water was added and the mixture was stirred at 25 ° C. for 30 minutes and then allowed to stand at 25 ° C. to separate the aqueous layer. I went twice. The obtained organic layer was dropped into 1000 g of hexane at 25 ° C. over 1 hour, and the precipitated solid was separated by filtration and dried under reduced pressure at 60 ° C. to obtain polymer (A1) [carbon-carbon two at the end of the methyl methacrylate block. 21.7 g of styrene-butadiene-methyl methacrylate triblock copolymer having a heavy bond].

As a result of GPC and ¹ H-NMR analysis, M _n = 6020 of polymer (A1), M _w / M _n = 1.03, M _n = 5040 of styrene block, M _n = 460 of butadiene block, methyl methacrylate block M _n = 520, introduction rate of carbon-carbon double bond at the end of the methyl methacrylate block = 78% ( ¹ H-NMR analysis value when 1,1,2,2-tetrachloroethane is used as an internal standard) there were.

(2) Synthesis of styrene-butadiene-methyl methacrylate triblock copolymer (A2) having a SAc group at the end of the methyl methacrylate block In a four-necked flask with an internal volume of 500 mL equipped with a stirrer and a thermometer, methanol was added. 110 g, 15.3 g of the polymer (A1) synthesized and purified above and 0.19 g (2.5 mmol) of thioacetic acid were added, and the mixture was stirred at 25 ° C. for 8 hours. The obtained reaction mixture was dropped into 500 g of hexane at 25 ° C. over 1 hour, and the precipitated solid was filtered off and dried under reduced pressure at 60 ° C. to obtain a polymer (A2) [SAc group at the end of the methyl methacrylate block. 16.1 g of a styrene-butadiene-methyl methacrylate triblock copolymer.

As a result of ¹ H-NMR analysis, the SAc group introduction rate at the end of the PMMA block was 78% (analysis value when 1,1,2,2-tetrachloroethane was used as an internal standard).

(3) Synthesis of styrene-butadiene-methyl methacrylate triblock copolymer (A3) having an SH group at the end of the methyl methacrylate block The inside of a 500 mL four-necked flask equipped with a stirrer and a thermometer The mixture was purged with nitrogen, 110 g of methanol, 15.9 g of the polymer (A2) synthesized and purified above and 0.14 g (2.5 mmol) of sodium methoxide were added, and the mixture was stirred at 25 ° C. for 2 hours. Thereafter, 0.15 g (2.5 mmol) of acetic acid was added to stop the reaction. To the reaction mixture, 200 g of toluene and 200 g of distilled water were added, and the mixture was stirred at 25 ° C. for 30 minutes and then allowed to stand at 25 ° C. to separate the aqueous layer five times. The mixture was added dropwise at 1 ° C. over 1 hour, and the precipitated solid was filtered off and dried under reduced pressure at 60 ° C., and polymer (A3) [triblock of styrene-butadiene-methyl methacrylate having an SH group at the end of the methyl methacrylate block. Copolymer] 15.5 g was obtained.

As a result of ¹ H-NMR analysis, the SH group introduction rate at the end of the PMMA block was 78% (analysis value when 1,1,2,2-tetrachloroethane was used as an internal standard).

<Example 2>
The same operation as in Example 1 was performed except that 19.5 mmol of n-butyl acrylate was used instead of 19.5 mmol of methyl methacrylate in Example 1 (1), and polymer (A4) [n-butyl acrylate] was obtained. 18.6 g of a triblock copolymer of styrene-butadiene- (n-butyl acrylate) having SH groups at the end of the block].

As a result of GPC and ¹ H-NMR analysis, M _n = 6210 of polymer (A4), M _w / M _n = 1.03, M _n = 5110 of styrene block, M _n = 450 of butadiene block, acrylic acid n- _M n = 650 butyl block, with SH group introduction rate to acrylic acid n- butyl block end = 81% ⁽¹ H-NMR analysis values at the time of the internal standard 1,1,2,2-tetrachloroethane) there were.

<Example 3>
In Example 1 (1), the same operation as in Example 1 was performed except that 39.0 mmol of 2,3-dimethyl-1,3-butadiene was used instead of 39.0 mmol of butadiene, and polymer (A5) [methacrylic acid] 15.8 g of styrene- (2,3-dimethyl-1,3-butadiene) -methyl methacrylate triblock copolymer] having SH groups at the ends of the acid methyl block.

As a result of GPC and ¹ H-NMR analysis, M _n = 5990 of polymer (A5), M _w / M _n = 1.03, M _n = 5330 of styrene block, 2,3-dimethyl-1,3-butadiene block of _M n = 330, methyl methacrylate block _M n = 330, ¹ H at the time of the internal standard SH group introduction rate = 79% (1,1,2,2-tetrachloroethane to the methyl methacrylate block end -NMR analysis value).

<Example 4>
In Example 1 (1), the same operation as in Example 1 was performed except that 19.5 mmol of methyl acrylate was used instead of 19.5 mmol of methyl methacrylate, and polymer (A6) [at the end of the methyl acrylate block] 17.0 g of a styrene-butadiene-methyl acrylate triblock copolymer having SH groups].

As a result of GPC and ¹ H-NMR analysis, M _n = 6170 of polymer (A6), M _w / M _n = 1.03, M _n = 5080 of styrene block, M _n = 500 of butadiene block, methyl acrylate block M _n = 590, SH group introduction rate at the end of the methyl acrylate block = 78% ( ¹ H-NMR analysis value when 1,1,2,2-tetrachloroethane was used as an internal standard).

<Example 5>
The same operation as in Example 1 was performed except that 9.8 mmol of 8-bromo-1-octene was used instead of 9.8 mmol of 7-octenylaldehyde in Example 1 (1), and polymer (A7) [methacrylic acid] 16.6 g of a styrene-butadiene-methyl methacrylate triblock copolymer having SH groups at the ends of the acid methyl block].

As a result of GPC and ¹ H-NMR analysis, the polymer (A7) had M _n = 6090, M _w / M _n = 1.03, the styrene block M _n = 5030, the butadiene block M _n = 550, and the methyl methacrylate block. M _n = 510, SH group introduction rate at the methyl methacrylate block end = 86% ( ¹ H-NMR analysis value when 1,1,2,2-tetrachloroethane was used as an internal standard).

<Example 6>
(1) Synthesis of methyl methacrylate homopolymer (A8) having a carbon-carbon double bond at the end In Example 1 (1), the operation of adding a cyclohexane solution containing cyclohexane, styrene and butadiene was omitted, Except for adding 233.7 mmol of methyl methacrylate instead of 19.5 mmol, the same operation as in Example 1 was carried out, and polymer (A8) [homopolymer of methyl methacrylate having a carbon-carbon double bond at the terminal] 22.4 g was obtained.

As a result of GPC and ¹ H-NMR analysis, the polymer (A8) had M _n = 6230, M _w / M _n = 1.03, carbon-carbon double bond introduction rate at the terminal = 91% (1,1,2, , 2-tetrachloroethane as an internal standard, ¹ H-NMR analysis value).

(2) Synthesis of methyl methacrylate homopolymer (A9) having a SAc group at the end In a 500 mL four-necked flask equipped with a stirrer and a thermometer, 120 g of methanol, the polymer synthesized and purified as described above ( A8) 11.3 g and thioacetic acid 0.14 g (1.8 mmol) were added and stirred at 25 ° C. for 8 hours. The obtained reaction mixture was dropped into 1000 g of hexane at 25 ° C. over 1 hour, the precipitated solid was filtered off and dried under reduced pressure at 60 ° C., and polymer (A9) [methyl methacrylate having SAc group at the terminal was obtained. The homopolymer of 11.8 g was obtained.

As a result of ¹ H-NMR analysis, the SAc group introduction rate at the terminal was 92% (analyzed value when 1,1,2,2-tetrachloroethane was used as an internal standard).

(3) Synthesis of methyl methacrylate homopolymer (A10) having an SH group at the end The inside of a 500 mL four-necked flask equipped with a stirrer and a thermometer was purged with nitrogen, and 100 g of methanol was synthesized above. Then, 10.1 g of purified polymer (A9) and 87.6 mg (1.6 mmol) of sodium methoxide were added, and the mixture was stirred at 25 ° C. for 2 hours. The reaction was stopped by adding 96.1 mg (1.6 mmol) of acetic acid. 200 g of toluene and 200 g of distilled water were added to the reaction mixture, and the mixture was stirred at 25 ° C. for 30 minutes and then allowed to stand at 25 ° C. to separate the aqueous layer 5 times. The obtained organic layer was dropped into 1000 g of hexane at 25 ° C. over 1 hour, the precipitated solid was separated by filtration and dried under reduced pressure at 60 ° C., and polymer (A10) [methyl methacrylate having an SH group at the terminal] 9.9 g of a homopolymer] was obtained.

As a result of ¹ H-NMR analysis, the SH group introduction rate at the terminal was 93% (analyzed value when 1,1,2,2-tetrachloroethane was used as an internal standard).

<Example 7>
The inside of a 500 mL four-necked flask equipped with a stirrer and a thermometer was purged with nitrogen, 190 g of toluene, 6.1 g of the polymer (A1) synthesized and purified in Example 1 (1), azobisisobutyro Nitrile 57.7 mg (0.3 mmol) and 3,6-dioxa-1,8-octanedithiol 0.91 g (5.0 mmol) were added and stirred at 60 ° C. for 3 hours. The reaction mixture was dropped into 600 g of methanol at 25 ° C. over 1 hour, and the precipitated solid was filtered off and dried under reduced pressure at 60 ° C. to obtain polymer (A11) [styrene having an SH group at the end of the methyl methacrylate block. -Butadiene-methyl methacrylate triblock copolymer] was obtained.

As a result of GPC and ¹ H-NMR analysis, the polymer (A11) had M _n = 6210, M _w / M _n = 1.03, and the SH group introduction rate at the end of the methyl methacrylate block = 86% (1,1,2, , 2-tetrachloroethane as an internal standard, ¹ H-NMR analysis value).

<Example 8>
The same operation as in Example 11 was performed except that 9.9 g of the polymer (A8) was used instead of 6.1 g of the polymer (A1) in Example 7, and the polymer (A12) [methacrylate having an SH group at the terminal, 10.6 g of methyl acid homopolymer].

As a result of GPC and ¹ H-NMR analysis, M _n = 6410 of polymer (A12), M _w / M _n = 1.03, SH group introduction rate at the terminal = 91% (1,1,2,2-tetra ¹ H-NMR analysis value when chloroethane was used as an internal standard).

(Pre-pattern formation on the base substrate)
Plasma Etch Inc. A styrene homopolymer having a terminal hydroxyl group (M _n = 6000, manufactured by Polymer Source Inc.) on an oxygen plasma-treated substrate (hereinafter referred to as “matrix substrate”) using a PE-200 benchtop plasma system manufactured by PE. (Hereinafter referred to as “PS-OH”) to form a film having a thickness of 40 nm, followed by annealing by heating at 160 ° C. for 24 hours under vacuum. Excess PS-OH was removed by ultrasonic cleaning in toluene, and a PS brush layer having a thickness of approximately 4.1 nm was formed. A photoresist film having a thickness of 50 nm was deposited on the PS brush layer with a 1.5 wt% PMMA (Mn = 950000, purchased from Micro Chem Inc.) chlorobenzene solution, and baked at 160 ° C. for 1 minute. Subsequently, electron beam lithography was performed through a mask so that Ls = 50 nm. At this time, electron beam lithography is described in J. Org. C. An LEO 1550BP SEM equipped with a Nabity pattern generation method was used and an acceleration voltage of 20 kV was used. The exposed base substrate was developed by being immersed in a 1: 3 volume ratio of methyl isobutyl ketone / isopropanol solution for 1 minute, and then the base substrate was washed with isopropanol. The obtained base substrate was subjected to oxygen plasma treatment and then stripped of PMMA photoresist with a warmed chlorobenzene solution, so that the portion of the PS brush layer modified by oxygen plasma was not modified into the PMMA domain. A pre-pattern (chemical guide) in which the portion has affinity for the PS domain was formed.

(Preparation of self-assembled composition containing polymer ink)
Polymer ink-containing self-assembled compositions (Compositions 1 to 11) were prepared at the composition ratios shown in Table 1.

(Formation of self-assembled film on base substrate with chemical guide)
Compositions 1 to 11 were applied onto a base substrate on which a chemical guide was formed, a film of about 50 nm was deposited, and annealing was performed at 190 ° C. for 24 hours under vacuum.

(MTP process)
Oxygen plasma treatment is performed on another substrate (hereinafter referred to as “transfer target substrate”) and placed on a self-assembled film formed using the above compositions 1-18 so that the substrates are parallel to each other. Fixed. Thereafter, annealing was performed at 160 ° C. for 24 hours under vacuum.
Thereafter, ultrasonic cleaning in chlorobenzene was performed to remove the block copolymer and unreacted polymer ink between the substrates, and the transferred substrate placed on the self-assembled film was peeled off. The same pattern as the self-assembled film formed on the base substrate was transferred to the obtained substrate to be transferred.

(Formation of self-assembled film on transfer substrate)
A 1.5 wt% toluene solution of PS-b-PMMA ( _{Mn of} styrene block and methyl methacrylate block is both 52000) is applied on the substrate to be transferred, and annealing is performed at 190 ° C. for 24 hours under vacuum. An organized membrane was formed.

(Reuse of mother board)
Apply a composition 1-11 according to the shape of the chemical guide on the base substrate after removing the self-assembled film, deposit a film of about 50 nm, and perform annealing at 190 ° C. for 24 hours under vacuum. Thus, a self-assembled film could be formed again on the base substrate.

<Evaluation Examples 1 to 11>
The pattern of the self-assembled film on the base substrate was observed using a length measurement SEM (S-4800, manufactured by Hitachi High-Technologies Corporation), and the width of the groove portion that appeared black was measured. The same observation was made on the self-assembled film on the substrate to be transferred, and the difference in width between the groove portions was evaluated. Furthermore, the self-assembled film on the transfer substrate was observed from above the pattern using a scanning electron microscope (CG4000, manufactured by Hitachi High-Technologies Corporation), and the line width of the pattern was measured at any 10 points. A 3-sigma value as a distribution degree was determined from the measured line width, and this value was defined as LWR (nm).

  Table 2 shows the evaluation results of the microphase separation structure width and LWR.

As shown in Table 2, when the polymer of the present invention (A3 to A7, A10 to 12) is used as the polymer ink, a pattern with a low LWR is obtained as compared with the case of using PS-OH or PMMA-OH. Was found to form.
That is, the polymer of the present invention is a polymer capable of transferring a pattern based on the microphase separation structure on the base substrate more faithfully onto another substrate.

  The polymer and the pattern forming method of the present invention are suitably used for lithography processes in the production of various electronic devices such as semiconductor devices and liquid crystal devices for which further miniaturization is required.

11 Substrate (matrix substrate)
12 Pre-pattern 13 Mixed polymer film 14 Self-assembled film 15 Substrate (substrate to be transferred)
16 Pre-pattern (chemical guide) formed by transferred polymer ink
17 Self-assembled film 17a PS phase 17b PMMA phase

Claims (9)

A polymer having a structure represented by the following general formula (1).
(In the formula, * represents a bond with another atom, B ³ represents a polymer block composed of a structural unit derived from (meth) acrylic acid ester, W represents a nitrogen atom, an oxygen atom and an arbitrary position) Represents a C2-61 divalent hydrocarbon group which may contain a sulfur atom.) The polymer of Claim 1 shown by following General formula (2).
(In the formula, B ¹ represents a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and B ² represents a structure derived from a conjugated diene. A polymer block consisting of a unit or a structural unit derived from a diphenylethylene derivative, B ³ represents a polymer block consisting of a structural unit derived from a (meth) acrylic acid ester, W is a nitrogen atom, oxygen at an arbitrary position Represents a divalent hydrocarbon group having 2 to 61 carbon atoms which may contain an atom and a sulfur atom, and m and n each independently represents 0 or 1.) The polymer according to claim 2, wherein m and n are 0. The polymer according to any one of claims 1 to 3, wherein B ³ is a polymer block synthesized by an anionic polymerization method comprising a structural unit derived from a (meth) acrylic acid ester. The polymer according to any one of claims 1 to 4, wherein W is represented by the following general formula (3).
(In the formula, ** represents a bond to B ³ , *** represents a bond to SH, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X represents a hydrogen atom. Alternatively, it represents a hydroxyl group, and W ¹ represents a C 1-50 divalent hydrocarbon group or a single bond that may contain a nitrogen atom, an oxygen atom and a sulfur atom at any position. The following general formula (4)
(In the formula, B ¹ represents a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and B ² represents a structure derived from a conjugated diene. A polymer block composed of units or a structural unit derived from a diphenylethylene derivative, B ³ represents a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and R ^{1 to} R ⁴ represent a hydrogen atom or carbon Represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a hydrogen atom or a hydroxyl group, and W ² represents a hydrocarbon group having 1 to 9 carbon atoms or a single atom which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position. And m and n each independently represents 0 or 1. R ² and R ³ may be bonded to each other to form a cyclic structure.)
A polymer represented by the following general formula (5)
(Wherein R ⁵ represents a hydrocarbon group having 1 to 10 carbon atoms)
Is reacted with the thiocarboxylic acid represented by the following general formula (6):
(In the formula, B ^{1 to} B ³ , R ^{1 to} R ⁵ , X, W ² , m, and n are as defined above.)
6. The method for producing a polymer according to claim 5, wherein the polymer represented by the formula (1) is synthesized and the polymer is treated under acidic or basic conditions. The following general formula (4)
(In the formula, B ¹ represents a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and B ² represents a structure derived from a conjugated diene. A polymer block composed of units or a structural unit derived from a diphenylethylene derivative, B ³ represents a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and R ^{1 to} R ⁴ represent a hydrogen atom or carbon A hydrocarbon group having 1 to 10 carbon atoms, X represents a hydrogen atom or a hydroxyl group, and W ² is a divalent hydrocarbon having 1 to 9 carbon atoms which may contain a nitrogen atom, an oxygen atom and a sulfur atom at any position. And m and n each independently represents 0 or 1. R ² and R ³ may be bonded to each other to form a cyclic structure.)
And a polymer represented by the following general formula (7)
(W ⁴ represents a C 1-9 divalent hydrocarbon group which may contain a nitrogen atom, an oxygen atom and a sulfur atom at an arbitrary position.)
The method for producing a polymer according to claim 5, wherein the dithiol represented by the formula is reacted. A polymer represented by the following general formula (4).
(In the formula, B ¹ represents a polymer block composed of a structural unit derived from a vinyl aromatic compound or a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and B ² represents a structure derived from a conjugated diene. A polymer block composed of units or a structural unit derived from a diphenylethylene derivative, B ³ represents a polymer block composed of a structural unit derived from a (meth) acrylic acid ester, and R ^{1 to} R ⁴ represent a hydrogen atom or carbon A hydrocarbon group having 1 to 10 carbon atoms, X represents a hydrogen atom or a hydroxyl group, and W ² is a divalent hydrocarbon having 1 to 9 carbon atoms which may contain a nitrogen atom, an oxygen atom and a sulfur atom at any position. And m and n each independently represents 0 or 1. R ² and R ³ may be bonded to each other to form a cyclic structure.) Step 1 for producing a base substrate having a pre-pattern;
Step 2 of forming a self-assembled film on the base substrate using a composition comprising a block copolymer that performs self-assembly and the polymer of any one of claims 1 to 5;
After bringing the surface of another substrate into contact with the surface of the self-assembled film formed on the base substrate, the other substrate is peeled off, and a part of the polymer of the present invention is placed on the surface of the other substrate. Moving step 3;
Applying a self-assembled composition containing a block copolymer on the surface of the other substrate to form a self-assembled film;
And 5 for removing a part of the phase of the self-assembled film;
A pattern forming method including: