TWI596124B - Block copolymer - Google Patents

Description

Block copolymer

This invention relates to block copolymers and their use.

The block copolymer has a molecular structure in which polymer subunits having a structure different from each other chemically are linked by a covalent bond. The block copolymer is capable of forming a periodically aligned structure, such as a sphere, cylinder or sheet, via phase separation. The domain size of the structure formed by self-assembly of the block copolymer can be adjusted over a wide range, and structures of various shapes can be prepared. Thus, these can be utilized in lithography patterning methods, various magnetic recording media or next generation nanodevices such as metal dots, quantum dots or nanowires, high density magnetic storage media, and the like.

The present invention provides a block copolymer, a polymer layer including the block copolymer, a method of forming a polymer layer, and a pattern forming method.

The block copolymer can include a first block and a second block different from the first block. The block copolymer may be a diblock copolymer comprising only the first and second blocks described above or may be a block copolymer comprising an additional block in addition to the first and second blocks.

The block copolymer can be phase separated because it comprises two or more polymer chains joined to each other via a covalent bond. In the present invention, since the block copolymer satisfies at least one of the following parameters, phase separation can occur very efficiently, and thus it can be microphase-separated to form a nano-scale structure. According to the present invention, the size or shape of the nanostructure can be freely adjusted by controlling the size such as the molecular weight or the relative ratio between the blocks. The block copolymer can freely form phase-separated structures of various sizes by the above, such as spheres, cylinders, gyroids, sheets and inverted structures, and the like. The inventors have found that if the block copolymer satisfies at least one of the following parameters, the self-assembly properties and phase separation properties as described above can be greatly improved. It has been confirmed that it is possible to cause the block copolymer to exhibit vertical alignment properties by satisfying the block copolymer with appropriate parameters. The term "vertical alignment property" as used herein may refer to the alignment properties of a block copolymer and may refer to an example in which the nanostructure formed by the block copolymer is oriented perpendicular to the substrate. Techniques for controlling the vertical or parallel alignment of self-assembled structures of block copolymers with respect to various substrates are a significant part of the practical application of block copolymers. The alignment direction of the nanoscale structure in the block copolymer layer is conventionally dependent on which of the blocks forming the block copolymer is exposed to the surface or air. In general, because many substrates are polar and air is non-polar The block, which has a higher polarity than the other blocks in the block copolymer, wets on the substrate and has a lower polarity than the other blocks in the block copolymer wets the interface between the air. A number of techniques have been proposed for simultaneously wetting substrates with blocks having different properties of the block copolymers, and the most typical method is to control alignment by preparing a neutral surface. However, in one embodiment, the block copolymer can be vertically aligned relative to the substrate by controlling the following parameters without conventionally known processing to achieve vertical alignment, including neutral surface treatment. For example, a block copolymer according to one embodiment of the present invention can exhibit vertical alignment properties on both a hydrophobic surface and a hydrophilic surface that have not been subjected to any pretreatment. Furthermore, in other embodiments, vertical alignment with respect to large areas can be achieved in a short time by thermal annealing.

The block copolymer can exhibit at least one peak within a predetermined range of the scattering vector (q) in an XRD (X-ray diffraction) analysis.

In one embodiment aspect, when XRD, the block copolymer can display at least one peak at 0.5 nm from the scattering vector (q value) of ¹ to 10 nm ^-1 range. In other embodiments, the scattering vector (q value) in which at least one peak is observed may range from 0.7 nm ^-1 or greater, 0.9 nm ^-1 or greater, 1.1 nm ^-1 or Larger, 1.3 nm ^-1 or greater, or 1.5 nm ^-1 or greater. In other embodiments, the scattering vector (q value) in which at least one peak is observed may range from 9 nm to ¹ or less, 8 nm to ¹ or less, 7 nm to ¹ or Smaller, 6 nm ^-1 or less, 5 nm ^-1 or less, 4 nm ^-1 or less, 3.5 nm ^-1 or less, or 3 nm ^-1 or less.

FWHM of the peak observed in the scattering vector (q) range (FWHM) can be from 0.2 nm ^-1 to 0.9 nm ^-1. In another embodiment, the FWHM can be 0.25 nm ^-1 or greater, 0.3 nm ^-1 or greater, or 0.4 nm ^-1 or greater. In another embodiment, the FWHM can be 0.85 nm ^-1 or less, 0.8 nm ^-1 or less, or 0.75 nm ^-1 or less.

The term 〝FWHM (full width at half maximum) as used herein may refer to the width of the peak (the difference between the scattering vectors (q)) showing the intensity being half of the maximum intensity.

In the XRD analysis, the scattering vectors (q) and FWHM are values for numerical analysis of the results of the XRD analysis described below, using the least squares technique. In the above method, the Gaussian fitting of the peak profile in the XRD pattern is performed in a state where the position of the XRD diffraction pattern having the lowest intensity becomes the reference line and the lowest intensity is converted into zero, and then The results of Gaussian fitting obtain the scattering vector (q) and FWHM. The Gaussian fit has an R square of at least 0.9 or greater, 0.92 or greater, 0.94 or greater, or 0.96 or greater. A method of obtaining the above information from XRD analysis is known, and for example, a numerical analysis program such as the origin can be used.

The block copolymer showing a peak of the above FWHM having the above-described scattering vector (q) may include a crystallized site suitable for self-assembly. A block copolymer showing a peak of the above FWHM in the range of the above scattering vector (q) can exhibit excellent self-assembly properties.

XRD analysis can be performed by passing X-rays through a block copolymer And then proceeding by measuring the scattering intensity from the scattering vector. XRD analysis of the block copolymer without any particular pretreatment can be performed, and for example, the analysis can be carried out by drying the block copolymer under appropriate conditions and then passing X-rays. X-rays having a vertical size of 0.023 mm and a horizontal size of 0.3 mm can be used as the X-rays. A 2D diffraction pattern that is scattered from the sample as an image is obtained by using a measuring device (for example, 2D marCCD), and then the above-described fitting with respect to the obtained diffraction pattern is performed in order to obtain a scattering vector and FWHM and the like.

The above parameters can be achieved by controlling the structure of the block copolymer.

For example, a block copolymer that satisfies the above parameters may include a side chain in the first block or the second block. For convenience of explanation, a block including a side chain may be referred to as a first block hereinafter.

As used herein, the term "anthracene of a fluorene-forming chain" refers to an atom that forms an atom attached to a side chain of a block copolymer and a linear structure that forms a side chain. The side chains may have a linear or branched structure; however, the number of atoms forming the chain is calculated only by the number of atoms forming the longest straight chain. Therefore, in the case where the atom in which the chain is formed is a carbon atom, the other atoms are not counted as the number of atoms forming the chain, such as a hydrogen atom bonded to a carbon atom and the like. Furthermore, in the case of a branched chain, the number of atoms forming a chain is the number of atoms forming the longest chain. For example, the chain is n-pentyl, all of the atoms forming the chain are carbon atoms and the number is 5. If the chain is a 2-methylpentyl group, all of the atoms forming the chain are also carbon atoms and the number is 5. The atoms forming the chain may be carbon, oxygen, sulfur or nitrogen and the like, and the proper formation of the chain The sub may be carbon, oxygen or nitrogen; or carbon or oxygen. The number of atoms forming the chain may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of atoms forming the chain may be 30 or less, 25 or less, 20 or less, or 16 or less.

In another embodiment, one or both of the first block and the second block of the block copolymer satisfying the above parameters may include at least an aromatic structure. Both the first block and the second block may comprise an aromatic structure, and in this example, the aromatic structure in the first block may be the same or different than the aromatic structure in the second block. Further, at least one of the first and second blocks of the block copolymer satisfying the parameters described in this document may include a side chain or at least one halogen atom as described below, and such a side chain or at least A halogen atom may be substituted by an aromatic structure. The block copolymer can include two or more blocks.

As stated, the first block and/or the second block of the block copolymer can comprise an aromatic structure. Such an aromatic structure can be included in one or both of the first block and the second block. In examples where both of the blocks include an aromatic structure, the aromatic structure in the first block may be the same or different than the aromatic structure in the second block.

The term "fluorene-aromatic structure" as used herein may mean aryl or extended aryl, and may be taken to include a benzene ring structure or at least two benzene rings thereof to share one or two carbon atoms or a random linking group. A monovalent or divalent substituent derived from a compound of a linked structure, or a derivative of a compound. The aryl or extended aryl group may be an aryl group having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms unless otherwise defined. from Monovalent or divalent substituents derived from benzene, naphthalene, azobenzene, anthracene, phenanthrene, fused tetraphenyl, anthracene, benzopyrene and the like may be exemplified by aryl or extended aryl groups.

The aromatic structure may be a structure included in the main chain of the block or may be a structure in which a side chain is bonded to the main chain of the block. For example, the adjustment of the parameters can be achieved by appropriately adjusting the aromatic structure that can be included in each block.

For example, to control the parameters, a chain having 8 or more chains forming an atom may be attached as a side chain to the first block of the block copolymer. In this document, the terms 〝 side chain 〝 and the term 〝 chain 〞 can indicate the same subject. In examples where the first block comprises an aromatic structure, the chain can be attached to an aromatic structure.

The side chain can be a chain that is attached to the backbone of the polymer. As noted, the side chains can be chains comprising 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more chains forming atoms. The number of atoms forming the chain may be 30 or less, 25 or less, 20 or less, or 16 or less. The atoms forming the chain can be carbon, oxygen, nitrogen or sulfur, or suitably carbon or oxygen.

The side chain can be a hydrocarbon chain such as an alkyl, alkenyl or alkynyl group. At least one carbon atom in the hydrocarbon chain may be replaced by a sulfur atom, an oxygen atom or a nitrogen atom.

In examples where a side chain is attached to an aromatic structure, the chain may be attached directly to the aromatic structure or may be attached to the aromatic structure via a linking group. The linking group may be an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, carbonyl, alkylene, alkenyl, alkynyl, -C(=O)-X ₁ - or - X ₁ -C(=O)-. In the above formula, R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S (= O) ₂ -, alkylene, alkenyl or alkynyl, and R ₂ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl. A suitable linking group can be an oxygen atom. The side chain can be attached to the aromatic structure via, for example, an oxygen atom or nitrogen.

In an example in which the aromatic structure is bonded as a side chain to the main chain of the block, the aromatic structure may be directly bonded to the main chain or may be bonded to the main chain via a linking group. The linking group may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, carbonyl, alkylene, alkenyl, alkynyl, -C(=O)-X ₁ - or -X ₁ -C ( =O)-. In the above formula, X ₁ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an extended alkynyl group. A suitable linking group for bonding the aromatic structure to the main chain may be -C(=O)-O- or -OC(=O)-, but is not limited thereto.

In another embodiment, the aromatic structure in the first block and/or the second block of the block copolymer may comprise 1 or more, 2 or more, 3 or more, 4 or more. Many, or 5 or more halogen atoms. The number of halogen atoms may be 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. The halogen atom may be fluorine or chlorine; and fluorine may be used. A block comprising an aromatic structure containing a halogen atom can effectively form a phase-separated structure by appropriate interaction with other blocks.

The aromatic structure having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms may be exemplified as an aromatic structure including a halogen atom, but is not limited thereto.

In order to achieve proper phase separation, in an example in which both the first and second blocks comprise an aromatic structure, the first block may include no The aromatic structure of the halogen atom and the second block may include an aromatic structure containing a halogen atom. Further, the aromatic structure of the first block may include a side chain linked directly or via a linking group including an oxygen or nitrogen atom.

In the example in which the block copolymer includes a block having a side chain, the block may be a block represented by, for example, Formula 1.

In Formula 1, R may be hydrogen or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkylene group. Alkyl, alkynyl, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, a stretched alkyl A base, an alkenyl group or an alkynyl group, and Y may be a monovalent substituent including a cyclic structure linked to a chain having 8 or more chains forming an atom.

The term 〝 single bond 如 as used herein may refer to an example in which no atom is in a corresponding position. For example, if X in Formula 1 is a single bond, a structure in which Y is directly bonded to a polymer chain can be realized.

The term "alkyl sulfonium" as used herein may mean a linear, branched or cyclic alkyl group having from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 8, or from 1 to 4 carbon atoms, unless otherwise Other definitions, and the alkyl group may be optionally substituted with at least one substituent. In the case where the side chain is an alkyl group, The alkyl group may include 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more carbon atoms, and the number of carbon atoms in the alkyl group may be 30 or less, 25 Or less, 20 or less, or 16 or less.

The term "decenyl or alkynyl" as used herein may mean a linear, branched or cyclic alkenyl group having from 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Or alkynyl, unless otherwise defined, and the alkenyl or alkynyl group is optionally substituted with at least one substituent. In the case where the side chain is an alkenyl or alkynyl group, the alkenyl or alkynyl group may include 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more carbon atoms, And the number of carbon atoms in the alkenyl or alkynyl group may be 30 or less, 25 or less, 20 or less, or 16 or less.

The term "alkyl" as used herein may refer to an alkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms unless otherwise defined. The alkylene group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term stilbene or alkynyl hydrazide as used herein may mean an alkenyl or alkynyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Unless otherwise defined. The alkenyl or alkynyl group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

In another embodiment, X in Formula 1 can be -C(=O)O- or -OC(=O)-.

Y in Formula 1 is a substituent including a chain, which may be a substituent including, for example, an aromatic structure having 6 to 18 or 6 to 12 carbon atoms base. In the above formula, the chain may be an alkyl group having 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more carbon atoms. The alkyl group can include 30 or less, 25 or less, 20 or less, or 16 or fewer atoms. The chain may be attached directly to the aromatic structure as described above or to the aromatic structure via a linking group.

In another embodiment, the first block can be represented by Formula 2.

In Formula 2, R may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X may be -C(=O)-O-, and P may be an extended aryl group having 6 to 12 carbon atoms. Q may be an oxygen atom, and Z is a chain having 8 or more atoms forming a chain.

In another embodiment of Formula 2, P can be a pendant phenyl group. Z may also be a linear alkyl group having 9 to 20, 9 to 18 or 9 to 16 carbon atoms. In the case where P is a phenylene group, Q may be bonded to the para position of the phenyl group. The alkyl group, the aryl group, the phenyl group and the chain may be optionally substituted with at least one substituent.

In the example in which the block copolymer includes a block containing an aromatic structure containing a halogen atom, the block may be a block represented by the following formula 3.

In Formula 3, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an alkynyl group, and W may be included At least one aryl group of a halogen atom.

In another embodiment of Formula 3, X ₂ can be a single bond or an alkylene group.

In Formula 3, the aryl group of W may be an aryl group having 6 to 12 carbon atoms or a phenyl group. The aryl or phenyl group may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. The number of halogen atoms may be 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. A fluorine atom can be used as the halogen atom.

In another embodiment, the block of Formula 3 can be represented by Formula 4 below.

[Formula 4]

In Formula 4, the X ₂ system is the same as defined in Formula 3, and R ₁ to R ₅ may each independently be a hydrogen, an alkyl group, a haloalkyl group or a halogen atom. The number of halogen atoms included in R ₁ to R ₅ is 1 or more.

In Formula 4, R ₁ to R ₅ may each independently be hydrogen, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms, or a halogen atom, and the halogen atom may be fluorine. Or chlorine.

In Formula 4, R ₁ to R ₅ may include 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more halogen atoms. The upper limit of the number of halogen atoms is not particularly limited, and the number of halogen atoms in R ₁ to R ₅ may be, for example, 12 or less, 8 or less, or 7 or less.

The block copolymer may include only the above two blocks, or may include one or both of the above two blocks and another block.

The method for preparing the block copolymer is not particularly limited. For example, block copolymers can be prepared by living radical polymerization (LRP). For example, there are methods such as anionic polymerization in which a block copolymer is in a mineral acid salt such as an alkali metal or alkaline earth metal salt. In the presence of an organic rare earth metal complex or an organic alkali metal compound as a polymerization initiator; an anionic polymerization reaction in which a block copolymer is synthesized using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound; Atom transfer radical polymerization (ATRP) using an atom transfer radical polymerizer as a polymerization control agent; ATRP by an electron transfer regeneration activator (ATGET) in the presence of an organic or inorganic reducing agent that generates electrons Polymerization using an atom transfer radical polymerization agent as a polymerization control agent; ATRP by a continuous activator regeneration initiator (ICAR); reversible addition using an inorganic reducing agent-reversible addition of a ring-opening chain transfer agent - Open-loop chain transfer (RAFT) polymerization; and a method using an organic ruthenium compound as an initiator, and an appropriate method can be selected among the above methods.

In one embodiment, the block copolymer can be prepared by a method comprising living a free radical polymerization of a material comprising a monomer capable of forming a block in the presence of a free radical initiator and a living radical polymerization reagent. polymerization. The method for preparing the block copolymer may additionally include, for example, precipitating the polymerization product formed by the above method in a non-solvent.

The kind of the radical initiator can be appropriately selected in consideration of the polymerization efficiency, and is not particularly limited, and an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-( 2,4-Dimethylvaleronitrile), or a peroxide compound such as benzhydryl peroxide (BPO) or di-tertiary butyl peroxide (DTBP).

LRP can be carried out in a solvent such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran Methane, dioxane, monoglyme, diglyme, dimethylformamide, dimethylhydrazine or dimethylacetamide.

As the non-solvent, for example, an alcohol such as methanol, ethanol, n-propanol or isopropanol, a diol such as ethylene glycol or an ether compound such as n-hexane, cyclohexane, n-heptane or petroleum ether can be used. no limit.

The block copolymers as described above exhibit excellent phase separation properties and self-assembly properties, and their vertical alignment properties are also excellent. The inventors have confirmed that the above properties can be further improved if the block copolymer additionally satisfies at least one of the following parameters.

For example, the block copolymer can form a layer on the hydrophobic surface that exhibits an in-plane phase diffraction pattern at a grazing incidence small angle X ray scattering (GISAXS). The block copolymer can form a layer on the hydrophilic surface that exhibits an in-plane phase diffraction pattern at a grazing angle incidence small angle X-ray scattering (GISAXS).

As used herein, the term "grain angle incident small angle X-ray scattering (GISAXS) shows in-plane phase diffraction pattern 〞 may refer to a peak perpendicular to the X coordinate observed on the GISAXS diffraction pattern when performing GISAXS analysis. example. Such peaks can be determined by the vertical alignment properties of the block copolymer. Therefore, the block copolymer showing the in-plane phase diffraction pattern exhibits a vertical alignment property. Furthermore, if the above-mentioned peaks having regular intervals are observed, the phase separation efficiency can be further improved.

The term "vertical" as used herein is a term that takes into account error and may, for example, include errors within ±10 degrees, ±8 degrees, ±6 degrees, ±4 degrees, or ±2 degrees.

A block copolymer capable of forming a layer exhibiting an in-plane phase diffraction pattern on both hydrophobic and hydrophilic surfaces can exhibit vertical alignment properties on various surfaces that are not subjected to any process that induces vertical alignment. The term "hydrophobic surface" as used herein may refer to a surface having a wet angle of purified water ranging from 5 degrees to 20 degrees. Examples of the hydrophobic surface may include a surface of a silicone treated with a piranha solution, sulfuric acid or oxygen plasma, but are not limited thereto. The term "hydrophilic surface" as used herein may refer to a surface having a wet angle of purified water ranging from 50 degrees to 70 degrees. Examples of the hydrophilic surface may include, but are not limited to, a polyfluorinated hydrogen fluoride, a polymethyloxy oxide treated with hexamethyldioxane, or a polydimethylsiloxane having a plasma treated with oxygen. .

In this document, properties that vary according to temperature, such as wetting angle, can be measured at room temperature unless otherwise defined. The term "room temperature" as used herein may refer to the temperature of its natural state that is not heated and cooled, and may refer to a temperature ranging from about 10 ° C to 30 ° C, or about 25 ° C or about 23 ° C.

The layer formed on the hydrophobic or hydrophilic surface and exhibiting the in-plane phase diffraction pattern on the GISAXS may be a layer that is thermally annealed. In one embodiment, the layer for measuring GISAXS is prepared, for example, by: diluting to a concentration of about 0.7% by weight of the block copolymer in a solvent (eg, fluorobenzene). The coating solution is applied to the corresponding hydrophobic or hydrophilic surface so that the coating has a thickness of about 25 nm and an area of about 2.25 square centimeters (width: 1.5 cm, length: 1.5 cm), and then Thermal annealing. Thermal annealing can be achieved by layering the layer at 160 ° C It is maintained for about 1 hour. GISAXS can be measured by irradiating the above prepared layer with X-rays having an incident angle in the range of from 0.12 to 0.23 degrees. The diffraction pattern from the layer scattering can be obtained by a conventional measuring device (for example, 2D marCCD). Techniques for confirming the presence of in-plane phase diffraction patterns from the diffraction patterns obtained above are known in the art.

The block copolymer showing the above peak in GISAXS can exhibit excellent self-assembly properties, and can be effectively controlled according to the target.

As described below, in the example in which at least one block of the block copolymer includes a side chain, the number of atoms forming the chain (n) and the scattering vector (q) obtained from the XRD analysis can satisfy the following equation.

[Equation 1] 3 nm ^-1 ~5 nm ^-1 = nq/(2×π)

In Equation 1, 〝n〞 is the number of atoms forming the chain, and 〝q〞 is the smallest scattering vector among the scattering vectors of the peaks observed in the XRD analysis or the scattering vector of the peak having the largest area observed. Furthermore, π in Equation 1 is the ratio of the circumference to its diameter.

The scattering vector and the like in Equation 1 above are values obtained by the same method as described in the XRD analysis.

The value of Equation 1 can be substituted scatter values in the range from 0.5 nm to 10 nm ^{-1 -1} of scatter values. In another aspect of the embodiment, the value of Equation 1 can be substituted scatter values in the range from 0.5 nm to 10 nm ^{-1 -1} of scatter values. In another embodiment, the scatter value substituted with the value of Equation 1 can be 0.7 nm ^-1 or greater, 0.9 nm ^-1 or greater, 1.1 nm ^-1 or greater, 1.3 nm ^{. 1} or greater, or 1.5 nm ^-1 or greater. In another aspect of the embodiment, the value of Equation 1 can be substituted scatter values ^-1 or less 9 nm, 8 ^nm-1 or less, 7 ^nm-1 or less, 6 nm ^{- 1} or less, 5 nm ^-1 or less, 4 nm ^-1 or less, 3.5 nm ^-1 or less, or 3 nm ^-1 or less.

Equation 1 may represent a relationship between the number of atoms forming a chain and the interval (D) between blocks including a chain in a state in which the block copolymer is self-assembled and forms a phase-separated structure. If the number of atoms forming the chain of the block copolymer including the chain satisfies Equation 1, the crystallizable property exhibited by the chain is improved, and thus the phase separation property and the vertical alignment property can be greatly improved. In another embodiment, nq/(2×π) in Equation 1 may be 4.5 nm ^-1 or less. In the above formula, the interval (D, unit: nanometer) between the blocks including the chain can be calculated by the numerical formula D = 2 × π / q. In the above formula, 〝D〞 is the interval between blocks (D, unit: nanometer), and π and q are the same as defined in Equation 1.

In one embodiment of the invention, the absolute difference between the surface energies of the first and second blocks may be 10 millinewtons per meter or less, 9 millinewtons per meter or less, 8 MilliNewtons/meter or less, 7.5 millinewtons/meter or less, or 7 millinewtons/meter or less. The absolute difference between the surface energies can be 1.5 millinewtons per meter or more, 2 millinewtons per meter or more, or 2.5 millinewtons per meter or more. The structure in which the first and second blocks in which the absolute difference between the surface energies are within the above range via the covalent bond can achieve effective microphase separation by phase separation due to appropriate incompatibility. In the above, the first block may be a block having a chain as described above.

The surface energy can be measured using a droplet shape analyzer (DSA100 product manufactured by KRUSS, Co.). In particular, the surface energy can be measured with respect to the layer produced by diluting to about 2% by weight solids in fluorobenzene with the sample to be measured (block copolymer or homopolymer) The coating solution prepared by the content is applied on the substrate so that the coating has a coating area of 50 nm and 4 cm 2 (width: 2 cm, length: 2 cm); coating at room temperature Drying is carried out for about 1 hour; and then thermal annealing is carried out at 160 ° C for about 1 hour. After the thermal annealing, a deionized water droplet of known surface tension is placed on the layer and then the contact angle is measured. The above method of obtaining the contact angle of deionized water was repeated 5 times, and the average of the obtained 5 contact angles was calculated. Similarly, after thermal annealing, a known surface tension of diiodomethane was dropped on the layer and then the contact angle was measured. The above method of obtaining the contact angle of diiodomethane was repeated 5 times, and the average of the obtained 5 contact angles was calculated. After that, the surface energy can be obtained by replacing the value of the surface tension of the solvent (Strom value) by the Owens-Wendt-Rabel-Kaelble method by using the average value of the contact angle obtained with deionized water and diiodomethane. The surface energy of each block in the block copolymer can be obtained by using the above method in relation to a homopolymer prepared from monomers forming the corresponding block.

In the example where the block copolymer comprises the above chain, the block comprising the chain may have a greater surface energy than the other blocks. For example, if the first block comprises a chain, the first block can have a greater surface energy than the second block. In this example, the surface energy of the first block can range from about 20 millinewtons per meter to about 40 millinewtons per meter. In another embodiment, The surface energy of the first block can be about 22 millinewtons per meter or more, about 24 millinewtons per meter or more, about 26 millinewtons per meter or more, or about 28 millinewtons per meter. Or bigger. The surface energy of the first block can be about 38 millinewtons per meter or less, about 36 millinewtons per meter or less, about 34 millinewtons per meter or less, or about 32 millinewtons per meter. Or smaller. Such a block copolymer comprising the above first block and exhibiting the above difference between the surface energies of the blocks can exhibit excellent self-assembly properties.

In the block copolymer, the absolute difference between the densities of the first and second blocks may be 0.25 g/cm 3 or more, 0.3 g/cm 3 or more, 0.35 g/cm 3 or more. Large, 0.4 g/cm 3 or larger, or 0.45 g/cm 3 or larger. The absolute difference between the densities may be 0.9 g/cm 3 or less, 0.8 g/cm 3 or less, 0.7 g/cm 3 or less, 0.65 g/cm 3 or less, or 0.6 g/ Cubic centimeters or less. The structure in which the first and second blocks in which the absolute difference between the densities are in the above range and which are linked via a covalent bond can achieve effective microphase separation by phase separation due to appropriate incompatibility.

The density of each block in the block copolymer can be obtained via known buoyancy methods. For example, it can be obtained by analyzing the mass of a block copolymer of mass and density known in air in a solvent such as ethanol.

In the case where the block copolymer contains the above side chain, the block containing the chain may have a lower density than the other blocks. For example, if the first block comprises a chain, the first block can have a lower density than the second block degree. In this example, the density of the first block can range from about 0.9 grams per cubic centimeter to about 1.5 grams per cubic centimeter. In another embodiment, the first block may have a density of about 0.95 grams per cubic centimeter or greater. The first block may have a density of about 1.4 grams per cubic centimeter or less, about 1.3 grams per cubic centimeter or less, about 1.2 grams per cubic centimeter or less, about 1.1 grams per cubic centimeter or less, or about 1.05 g/cm 3 or less. Such a block copolymer comprising the above first block and exhibiting the above difference between the densities of the blocks can exhibit excellent self-assembly properties. Surface energy and density are measured at room temperature.

The block copolymer may include a block having a volume fraction of from 0.4 to 0.8 and a block having a volume fraction of from 0.2 to 0.6. In the case where the block copolymer contains a chain, the block having a chain may have a volume fraction of from 0.4 to 0.8. For example, the first block comprises a chain, the first block may have a volume fraction of from 0.4 to 0.8 and the second block may have a volume fraction of from 0.2 to 0.6. The sum of the volume fractions of the first and second blocks may be one. The block copolymers each including each block having the above volume fraction can exhibit excellent self-assembly properties. The volume fraction of each block of the block copolymer can be obtained using the density of each block and the molecular weight obtained by gel permeation chromatography (GPC).

The block copolymer may have a number average molecular weight (Mn) ranging, for example, from about 3,000 to 300,000. The term 〝 number average molecular weight 〞 as used herein may refer to a conversion value relative to standard polystyrene measured by GPC (gel permeation chromatography). The term "molecular weight" as used herein may refer to a number average molecular weight unless otherwise defined. In another embodiment, the molecular weight (Mn) may be, for example, 3000 or more. 5000 or greater, 7000 or greater, 9000 or greater, 11,000 or greater, 13,000 or greater, or 15,000 or greater. In another embodiment, the molecular weight (Mn) may be, for example, 250,000 or less, 200,000 or less, 180,000 or less, 160,000 or less, 140,000 or less, 120,000 or less, 100,000 or less, 90000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, or 25,000 or less. The block copolymer may have a polydispersity (Mw/Mn) in the range of from 1.01 to 1.60. In another embodiment, the polydispersity can be about 1.1 or greater, about 1.2 or greater, about 1.3 or greater, or about 1.4 or greater.

Within the above range, the block copolymer can exhibit appropriate self-assembly properties. The number average molecular weight of the block copolymer and the like can be controlled in consideration of the self-assembled structure of the target.

If the block copolymer comprises at least the first and second blocks, the ratio of the first block (eg, including the blocks of the chain) in the block copolymer may range from 10 mole % to 90 mole % Within the scope.

The present invention is directed to a polymer layer comprising a block copolymer. The polymer layer can be used in a variety of applications. For example, it can be used in a biosensor, a recording medium such as a flash memory, a magnetic storage medium, or a pattern forming method, or an electric device or an electronic device and the like.

In one embodiment, the block copolymer in the polymer layer can form a periodic structure by self-assembly, including spheres, cylinders, pentagonal tetrahedrons or sheets. For example, the first block or the second block in the block copolymer or linked to other blocks of the above block via a covalent bond In one segment, the other segments may form a regular structure such as a sheet form, a cylinder form, and the like. Moreover, the above structure can be vertically aligned.

The polymer layer can exhibit the above-described in-plane phase diffraction pattern, that is, a peak perpendicular to the X coordinate in the GISAXS diffraction pattern of the GISAXS analysis. In other embodiments, two or more peaks are observed in the X coordinate of the GISAXS diffraction pattern. In the example in which two or more peaks are observed, the scattering vector (q value) can be confirmed with a constant ratio.

The invention also relates to a method of forming a polymer layer using a block copolymer. The method can include forming a polymer layer comprising a block copolymer in a self-assembled state on a substrate. For example, the method may include forming a layer of a block copolymer or a coating solution (in which the block copolymer is diluted in a suitable solvent) on a substrate by coating and the like, and then aging the layer if necessary. Or heat treated.

The aging or heat treatment can be carried out based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and can be carried out, for example, at a temperature higher than the glass transition temperature or the phase transition temperature. The time of the heat treatment is not particularly limited, and the heat treatment may be performed for about 1 minute to 72 hours, but may be changed if necessary. Further, the temperature of the heat treatment of the polymer layer may be, for example, 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer used herein.

The layer formed can be aged in a non-polar solvent and/or a polar solvent at room temperature for about 1 minute to 72 hours.

The invention also relates to a patterning method. The method can include The first or second block of the block copolymer is selectively removed from a laminate comprising a substrate and a polymer layer formed on the surface of the substrate and comprising a self-assembled block copolymer. The method can be a method of forming a pattern on the above substrate. For example, the method can include forming a polymer layer on the substrate, selectively removing one block or two or more blocks of the block copolymer in the polymer layer, and then etching the substrate. For example, a nano-scale micropattern can be formed by the above method. Further, depending on the shape of the block copolymer in the polymer layer, patterns of various shapes such as a nanorod or a nanopore can be formed by the above method. To form a pattern, the block copolymer can be mixed with another copolymer or homopolymer if necessary. The kind of the substrate to be applied to this method can be selected without particular limitation, and for example, ruthenium oxide and the like can be applied.

For example, according to this method, a ruthenium oxide nano-scale pattern having a high aspect ratio can be formed. For example, various types of patterns, such as nanorods or nanopore patterns, can be formed by forming a polymer layer on yttrium oxide, selectively removing a block copolymer in which the polymer layer is formed. Any one block of the block copolymer in a state of a predetermined structure, and ruthenium oxide is etched by various methods, such as reactive ion etching. Further, a nano pattern having a high aspect ratio can be formed according to the above method.

For example, the pattern can be formed on the order of tens of nanometers, and such a pattern can be applied to various uses, including a new generation of information electronic magnetic recording medium.

For example, a pattern in which a nanostructure (e.g., a nanowire) having a width of about 3 to 40 nm is disposed at intervals of about 6 to 80 nm can be formed by the above method. In another embodiment, it can be achieved therein A nanopore of about 3 to 40 nanometers in width (e.g., diameter) is configured at intervals of about 6 to 80 nanometers.

In addition, a nanowire or a nanopore having a high aspect ratio can be formed by this structure.

In this method, the method of selectively removing any one block of the block copolymer is not particularly limited, and may be removed using, for example, irradiation of a suitable electromagnetic wave (for example, ultraviolet rays) to the polymer layer. A relatively soft block method. In this example, the conditions of ultraviolet irradiation may be determined depending on the block type of the block copolymer, and may be irradiated with ultraviolet rays having a wavelength of about 254 nm for 1 to 60 minutes.

Additionally, after irradiation with ultraviolet light, the polymer layer can be treated with an acid to further remove the segment degraded by the ultraviolet light.

In addition, etching the substrate using the polymer layer selectively removing the block may be performed by reactive ion etching using CF ₄ /Ar ions, and after the above method, further processing by oxygen plasma may be performed from the substrate. Remove the polymer layer.

The present invention can provide block copolymers having excellent self-assembly and phase separation properties and thus can be effectively used in various applications. The invention also provides for the use of block copolymers.

Figures 1 to 6 show SEM images of polymer layers.

Figures 7 and 8 show the GISAXS diffraction pattern.

Figures 9 through 11 show SEM images of polymer layers.

Figures 12 through 14 show the GISAXS diffraction pattern.

Exemplary implementation

The invention will be described in detail below with reference to the examples and comparative examples, but the scope of the invention is not limited by the following examples.

NMR analysis

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The sample to be analyzed was used after it was diluted to a concentration of about 10 mg/ml in a solvent for NMR analysis (CDCl ₃ ), and the chemical shift (δ) was expressed in ppm.

<abbreviation>

Br = broad peak signal, s = single peak, d = double peak, dd = two double peaks, t = triplet, dt = two triplets, q = quartet, p = quartet, m = multiple peak

2. GPC (gel permeation chromatography)

The number average molecular weight and polydispersity are measured by GPC (gel permeation chromatography). The block copolymer or macroinitiator to be measured of the examples or comparative examples is placed in a 5 ml vial and then diluted to about 1 mg. /ml concentration. The standard sample for calibration and the sample to be analyzed were then filtered with a syringe filter (pore size: 0.45 μm) and then analyzed. ChemStation from Agilent technologies, Co. was used as the analysis program. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained by comparing the elution time of the sample with a calibration curve, and then obtaining a polydispersity (PDI) from the ratio (Mw/Mn). The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Device: 1200 series from Agilent technologies, Co.

Column: use two of PLgel mixed B from Polymer laboratories, Co.

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / ml, 200 L injection

Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

3. GISAXS (grazing angle incident small angle X-ray scattering)

The GISAXS analysis was performed in the 3C beam path of the Pohang Light Source. The coating solution was prepared by dissolving the block copolymer to be evaluated in fluorobenzene so as to have a solid content of 0.7% by weight, and the coating solution was spin-coated on the substrate so as to have a thickness of about 5 nm. The coated area is controlled to be about 2.25 square centimeters (coated area: width = 1.5 cm, long Degree = 1.5 cm). The coating was dried at room temperature for about 1 hour and then subjected to thermal annealing at about 160 ° C for about 1 hour to facilitate phase separation. Thus, a layer in which the phase separation structure is realized is formed. The formed layer is irradiated with X-rays such that the angle of incidence is from about 0.12 degrees to 0.23 degrees, which corresponds to the angle between the critical angle of the layer and the critical angle of the substrate, and then self-layer scattering is obtained by using a 2D marCCD. The X-ray diffraction pattern. At this point, the distance from the layer to the detector is selected to effectively observe the self-assembled pattern in the layer from about 2 meters to 3 meters. A substrate having a hydrophilic surface (a polymethoxyl plate treated with a piranha solution and having a wetting angle of about 5 degrees with respect to purified water at room temperature) or a substrate having a hydrophobic surface (with HMDS (hexamethyldiazine) As the substrate, a polydecyl oxide plate treated with a nitrogen alkane) having a wetting angle of about 60 degrees with respect to purified water at room temperature.

4. XRD analysis

The XRD pattern was evaluated by measuring the scattering intensity from the scattering vector (q) by passing X-rays through the sample in the 4C beam path of the Pohang Light Source. After the sample was placed in a bath for measuring XRD, a powder obtained without performing any specific pretreated block copolymer for purifying impurities was used as a sample. During the XRD pattern analysis, X-rays having a vertical size of 0.023 mm and a horizontal size of 0.3 mm were used as X-rays, and a measuring device (for example, 2D marCCD) was used as a detector. A 2D diffraction pattern that is image-scattered from the sample is obtained. Analysis of the obtained diffraction pattern using numerical analysis of the least squares technique In the case, obtain information such as the scattering vector and FWHM. The analysis is performed with the origin program. The position of the XRD diffraction pattern having the lowest intensity becomes the reference line and the lowest intensity is converted to zero, and then a Gaussian fitting is performed with respect to the peak profile in the XRD pattern, and then the scattering vector (q) is obtained from the result of the Gaussian fitting and FWHM. The R square of the Gaussian fit is set to 0.96 or more.

5. Surface energy measurement

The surface energy was measured using a drop shape analyzer (DSA 100 product from KRUSS, Co.). The surface energy is evaluated by a polymer layer formed by spin coating a coating solution prepared by dissolving the material to be evaluated in fluorobenzene so as to have a solid content of 2% by weight. Round so that the coating has a thickness of 50 nm (coating area: width = 2 cm, length = 2 cm), and the coating is allowed to dry at room temperature for about 1 hour, and then the coating is allowed to receive Thermal annealing at 160 ° C for about 1 hour. The method of deionized water droplets in which the surface tension is known is subjected to the layer after the thermal annealing and then the contact angle thereof is repeated 5 times, and the average of the obtained 5 contact angles is calculated. Similarly, the method in which the surface tension of diiodomethane was known to be dropped on the layer after the thermal annealing and then the contact angle thereof was obtained was repeated 5 times, and the average of the obtained 5 contact angles was calculated. The surface energy was obtained by the Owens-Wendt-Rabel-Kaelble method using the average of the contact angles obtained with deionized water and diiodomethane and substituting the value of the surface tension of the solvent (Strom value). The surface energy of each block of the block copolymer is prepared as described above with respect to the monomer formed only by the block. Obtained from a homopolymer.

6. Volume fraction measurement

The volume fraction of each block of the block copolymer is calculated based on the molecular weight measured by GPC (gel permeation chromatography) and the density at room temperature. In the above, the density is measured by the buoyancy method, especially by the mass of the sample to be measured, known in air, in the solvent (ethanol).

Preparation Example 1. Synthesis of Monomer (A)

The compound of the following formula A (DPM-C12) was synthesized by the following method. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were added to a 250 ml flask and dissolved in 100 ml of acetonitrile, and excess potassium carbonate was added thereto. The mixture was then reacted at 75 ° C under nitrogen for about 48 hours. After the reaction, the remaining potassium carbonate and acetonitrile used for the reaction were removed. A mixed solvent of dichloromethane (DCM) and water was added to carry out the work, and the separated organic layer was collected and dried over MgSO ₄ . A white solid intermediate having a yield of about 37% was then obtained via column chromatography using DCM.

<NMR analysis results of intermediates>

¹ H-NMR (CDCl ₃ ): δ 6.77 (dd, 4H); δ 4.45 (s, 1H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p , 2H); δ1.33-1.26(m, 16H); δ0.88(t, 3H)

The intermediate to be synthesized (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmol) and Dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) was placed in a flask, 120 ml of dichloromethane was added, and the reaction was carried out under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt produced in the reaction was removed via a filter, and the remaining dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as the mobile phase, and the obtained product was recrystallized in a mixed solvent of methanol and water (mixed in a weight ratio of 1:1), This gave a white solid product (DPM-C12) (7.7 g, 22.2 mmol) with 63% yield.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 0.88 (t, 3H)

In the above formula, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Monomer (G)

The compound of the following formula G was synthesized according to the method of Preparation 1, except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<Results of NMR analysis on DPM-C4>

_{^{1 H-NMR (CDCl 3)}} : δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.33 (dt, 1H); δ5.73 (dt, 1H); δ3.95 (t , 2H); δ2.06 (dd, 3H); δ 1.76 (p, 2H); δ 1.49 (p, 2H); δ 0.98 (t, 3H)

In the above formula, R is a linear alkyl group having 4 carbon atoms.

Preparation Example 3. Synthesis of Monomer (B)

The compound of the following formula B was synthesized according to the method of Preparation 1, except that 1-bromooctane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C8>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.45 (p, 2H); 1.33-1.29 (m, 8H); δ 0.89 (t, 3H)

In the above formula, R is a linear alkyl group having 8 carbon atoms.

Preparation Example 4

The compound of the following formula C (DPM-C10) was synthesized according to the method of Preparation 1, except that 1-bromodecane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C10>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.72 (dt, 1H); δ 3.94 (t) , 2H); δ2.06 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.34-1.28 (m, 12H); δ 0.89 (t, 3H)

In the above formula, R is a linear alkyl group having 10 carbon atoms.

Preparation Example 5

The compound of the following formula D was synthesized according to the method of Preparation 1, except that 1-bromotetradecane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C14>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.27 (m, 20H); δ 0.88 (t, 3H.)

In the above formula, R is a linear alkyl group having 14 carbon atoms.

Preparation Example 6

The compound of the following formula E is prepared according to the method of Preparation Example 1. In addition to using 1-bromohexadecane instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C16>

¹ H-NMR (CDCl ₃ ): δ 7.01 (dd, 2H); δ 6.88 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.26 (m, 24H); δ 0.89 (t, 3H)

In the above formula, R is a linear alkyl group having 16 carbon atoms.

Example 1

2.0 g of the compound of Preparation Example 1 (DPM-C12), 64 mg of RAFT (reversible addition-fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile) And 5.34 ml of benzene was added to a 10 ml flask and then stirred at room temperature for 30 minutes, and then subjected to RAFT (reversible addition fragmentation chain transfer) polymerization at 70 ° C for 4 hours. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, vacuum filtered and dried to obtain a pink macroinitiator. The yield of the macroinitiator is about 86%, and the number average molecular weight thereof (Mn) and polydispersity (Mw/Mn) were 9,000 and 1.16, respectively.

0.3 g of the giant initiator, 2.7174 g of pentafluorostyrene and 1.306 ml of benzene were added to a 10 ml Schlenk flask and then stirred at room temperature for 30 minutes, and then subjected to RAFT at 115 ° C for 4 hours (reversible addition) Fracture chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, vacuum filtered and dried to obtain a light pink block copolymer. The yield of the block copolymer was about 18%, and the number average molecular weight (Mn) and polydispersity (Mw/Mn) thereof were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the monomer (A) of Preparation Example 1 and a second block derived from pentafluorostyrene.

Example 2

The block copolymer was prepared in the same manner as in Example 1 except that the monomer (B) of Preparation Example 3 was used instead of the macroinitiator prepared by the monomer (A) of Preparation Example 1 and pentafluorostyrene. . The block copolymer includes a first block derived from the monomer (B) of Preparation Example 3 and a second block derived from pentafluorostyrene.

Example 3

The block copolymer was prepared in the same manner as in Example 1 except that the monomer (C) of Preparation Example 4 was used instead of the macroinitiator prepared by the monomer (A) of Preparation Example 1 and pentafluorostyrene. . The block copolymer includes the first block derived from the monomer (C) of Preparation Example 4 and from pentafluorobenzene The second block derived from ethylene.

Example 4

The block copolymer was prepared in the same manner as in Example 1 except that the monomer (D) of Preparation Example 5 was used instead of the macroinitiator prepared by the monomer (A) of Preparation Example 1 and pentafluorostyrene. . The block copolymer includes a first block derived from the monomer (D) of Preparation Example 5 and a second block derived from pentafluorostyrene.

Example 5

The block copolymer was prepared in the same manner as in Example 1, except that the macroinitiator prepared by using the monomer (E) of Preparation Example 6 instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. . The block copolymer includes a first block derived from the monomer (E) of Preparation Example 6 and a second block derived from pentafluorostyrene.

Comparative example 1

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator prepared by using the monomer (G) of Preparation Example 2 instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. . The block copolymer includes a first block derived from the monomer (G) of Preparation Example 2 and a second block derived from pentafluorostyrene.

Comparative example 2

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator prepared by using the monomer (A) of Preparation Example 1 and the pentafluorostyrene by using 4-methoxyphenyl methacrylate was used. other than. The block copolymer comprises a first block derived from 4-methoxyphenyl methacrylate and a second block derived from pentafluorostyrene.

Comparative example 3

The block copolymer was prepared in the same manner as in Example 1 except that a macroinitiator prepared by using the dodecyl methacrylate in place of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. The block copolymer comprises a first block derived from dodecyl methacrylate and a second block derived from pentafluorostyrene.

The GPC results for the macroinitiators and block copolymers of the examples are set forth in Table 1.

Test Example 1. XRD Analysis

About a block copolymer based on a result of the above-described methods performed by XRD analysis are set forth in 2 (in the example of Comparative Example 3, when not observed scattering from 0.5 nm to 10 nm ^{-1 -1} the vector scope of the following table To the peak).

Test example 1.

The self-assembled polymer layer is obtained by dissolving the block copolymer of the embodiment or the comparative example in fluorobenzene and spin-coating the coating solution on the tantalum wafer so that the coating thickness is 5 nm (coating area: width x length = 1.5 cm x 1.5 cm), and the coating was allowed to dry at room temperature for 1 hour, and then the coating was subjected to thermal annealing at about 160 ° C for 1 hour. An SEM (Scanning Electron Microscope) image of the formed polymer layer was then obtained. 1 to 5 are the results of Examples 1 to 5, respectively. As confirmed from the figure, in the example of the block copolymer of the example, a self-assembled polymer layer having a line pattern was efficiently formed. However, proper phase separation was not achieved in the comparative examples. For example, FIG. 6 is the SEM result of Comparative Example 3, and it was confirmed that effective phase separation was not achieved.

Test Example 2. Confirmation of GISAXS diffraction pattern

Figure 7 shows the results of a GISAXS (grazing angle incident small angle X-ray scattering) analysis of the block copolymer of Example 1 carried out on a hydrophilic surface having a contact angle of about 5 degrees with respect to purified water at room temperature, and Figure 8 shows the results of a GISAXS (grazing angle incident small angle X-ray scattering) analysis of the block copolymer of Example 1 carried out with a hydrophobic surface having a contact angle of about 60 degrees with respect to purified water at room temperature. It can be confirmed from Figures 7 and 8 that the in-plane phase diffraction pattern is observed in any of the examples. It can be confirmed from the above that the block copolymer can exhibit vertical alignment properties with respect to various substrates.

Further, a polymer layer can be formed by the same method as described above by using the block copolymer of Example 1. The polymer layer is formed by a guar solution treated with a piranha solution having a 5 degree purified water contact angle at room temperature, a cerium oxide substrate having a 45 degree purified water contact angle at room temperature, and 60 at room temperature. The HMDS (hexamethyldioxane) treated polydecyloxy plate was purified at a water contact angle. Figures 9 through 11 are SEM images of polymer layers on surfaces having contact angles of 5, 45 and 60 degrees, respectively. It can be confirmed from the figure that the block copolymer forms a phase-separated structure regardless of the surface properties of the substrate.

Test Example 3. Measurement of properties of block copolymer

The results of the evaluation of each block as measured by the above method are set forth in the following table.

Test Example 4.

Further, block copolymers having different volume ratios were obtained in the same manner as in Example 1, except that the molar ratio of the monomer to the macroinitiator was controlled.

The volume fraction is as follows.

The volume fraction of each block of the block copolymer is calculated based on the molecular weight measured by GPC (gel permeation chromatography) and the density at room temperature. In the above, the density is measured by a buoyancy method, in particular, by mass of a block copolymer of mass and density known in air in a solvent such as ethanol, and GPC is carried out according to the above method.

The polymer layer is obtained by spin coating a coating solution prepared by dissolving a block copolymer of each sample in fluorobenzene to a solid content of about 0.7% by weight on a tantalum wafer, so that The coating thickness was 5 nm (coating area: width = 1.5 cm, length = 1.5 cm), and the coating was allowed to dry at room temperature for 1 hour, and then the coating was subjected to acceptance at about 160 ° C. Hour thermal annealing. Next, GISAXS is performed and the results are exemplified in the figure. 12 to 14 are the results of the samples 1 to 3, respectively, and it was confirmed that the in-plane phase diffraction pattern was observed, and the block copolymer had a vertical alignment property.

Claims (10)

A block copolymer comprising a first block and a second block different from the first block, and exhibits the X-ray diffraction method, at least one of from 0.5 nm to 10 nm ^{-1 -1} the scattering vector (q) in the range of the half maximum full-width (full width at half maximum) from the peak lines ¹ to 0.2 nm of 1.5 nm ^-1, wherein the first block is represented by the following formula 1, which The second block is represented by the following formula 3: Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and Y is contained a monovalent substituent having a cyclic structure in which 8 or more chain-forming atoms are linked, wherein the cyclic structure is an aromatic structure having 6 to 18 carbon atoms, and wherein the chain-forming atom is carbon, Oxygen, sulfur or nitrogen; [Formula 3] Wherein X ₂ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms, and 2 to 20 An alkynyl group of a carbon atom, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ An alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and W is an aryl group containing at least one halogen atom. The patentable scope of application of the block copolymer of item 1, wherein the X-ray diffraction method is the scattering vector (g FWHM line peak from 0.2 nm to 1.5 nm ^{-1 -1} lies show ) ranging from 1 nm to 3 nm ^{-1 -1.} The patentable scope of application of the block copolymer of item 1, wherein the X-ray diffraction method, the half of the peak from 0.5 nm to 10 nm ^-1 scattering vector of ^-1 (q) show peak in the range of The full width is from 0.3 nm ^-1 to 0.9 nm ^-1 . The block copolymer according to claim 1, wherein the layer exhibits a layer exhibiting an in-plane phase diffraction pattern in a grazing incidence small angle X ray scattering. a block copolymer according to claim 1 of the scope of the patent application, wherein The number average molecular weight is from 3,000 to 300,000. The block copolymer according to the first aspect of the patent application, wherein the polydispersity (Mw/Mn) is from 1.01 to 1.60. A polymer layer comprising the self-assembled product of the block copolymer of claim 1 of the patent. A polymer layer according to claim 7 wherein the in-plane phase diffraction pattern is exhibited in a grazing angle incident small angle X-ray scattering method. A method of forming a polymer layer comprising forming a polymer layer comprising a self-assembled product of the block copolymer of claim 1 of the patent. A pattern forming method comprising selectively removing the block copolymer from a laminate comprising a substrate and a polymer layer formed on the substrate and comprising the self-assembled product of the block copolymer of claim 1 The first block or the second block of matter.