TWI596127B - Block copolymer - Google Patents

Description

Block copolymer

This application relates to block copolymers and their use.

The block copolymer has a molecular structure in which polymer subunits having different chemical structures are linked to each other by covalent bonds. The block copolymer is capable of forming a periodically aligned structure such as a sphere, a cylinder or a laminate via phase separation. The size of the structure formed by the self-assembly of the block copolymer can be adjusted within a wide range and can be made into various structural shapes. Therefore, they can be used for a method of forming a pattern by etching, various magnetic recording media or a new generation of nanodevices (such as metal dots, quantum dots or nanowires), high-density magnetic storage media, and the like.

The present application provides block copolymers, polymer layers comprising block copolymers, methods of forming polymer layers, and methods of forming patterns.

The present block copolymer comprises a first block and a second block different from the first block. The first or second block can include side chains as described below. Hereinafter, in the case where one block of the first and second blocks includes a side chain, a block including a side chain is referred to as a first block. The block copolymer may be a diblock copolymer comprising only the first and second blocks above or may be a block copolymer comprising additional blocks in addition to the first and second blocks.

Since the block copolymer contains two or more polymer chains linked to each other via a covalent bond, it can be phase separated. In the present application, since the block copolymer satisfies at least one of the parameters described below, phase separation can occur very efficiently, and thus a nano-sized structure can be formed by microphase separation. According to the present application, the size or shape of the nanostructure can be freely adjusted by controlling the size (e.g., molecular weight or relative ratio between blocks). By the above, the block copolymer can freely form phase-separated structures of various sizes such as a sphere, a cylinder, a spiral tetrahedron, and a laminate and an opposite structure. The inventors have found that if the block copolymer satisfies at least one of the parameters described below, the above self-assembly and phase separation properties can be greatly improved. It has been confirmed that the block copolymer can exhibit an upright alignment property by making the block copolymer satisfy appropriate parameters. As used herein, "upright alignment property" refers to the alignment properties of the block copolymer and may refer to a nano-sized structure formed by the block copolymer aligned in a direction perpendicular to the substrate. A major focus of the practical application of the block copolymers that control the alignment of the self-assembled structures of the block copolymers to be perpendicular or parallel to the various substrates. Conventionally, the orientation of the nano-size structure in the layer of the block copolymer depends on the formation of the block. A block in a block of a polymer that is exposed to a surface or air. Generally, since many substrates are polar and air is non-polar, blocks that are more polar than the other blocks in the block copolymer wet the substrate and are less polar than the other blocks in the block copolymer. The interface between the air. Therefore, many techniques have been proposed to cause blocks of different properties in the block copolymer to face the substrate simultaneously, and the most common method is to control the alignment by fabricating a neutral surface. However, in one embodiment, the block copolymers can be aligned perpendicular to the substrate by controlling the following parameters, and generally known treatments for achieving upright alignment, including neutral surface treatments, are not performed. For example, a block copolymer according to one embodiment of the present application exhibits an upright alignment property on both a hydrophobic surface and a hydrophilic surface that have not been subjected to any pretreatment. In addition, in another specific embodiment, the heat is returned to the temperature, and the vertical arrangement is realized in a short time in a large area.

The block copolymer according to the present application exhibits a specific tendency in XRD (X-ray diffraction) analysis.

That is, as described below, in the case where at least one block of the block copolymer includes a side chain, the number of chain-forming atoms (n) and the scattering vector (q) obtained by XRD analysis satisfy the following Equation 1.

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

In Formula 1, "n" is the number of chained atoms, and "q" is the smallest scattering vector in the scattering vector at the peak observed in the XRD analysis or the scattering vector at the peak having the largest area observed. Further, π in Equation 1 is the ratio of the circumference to its diameter.

As used herein, "chain-forming atom" refers to an atom that forms an atom that links to a side chain of a block copolymer and a linear structure that forms a side chain. This chain may have a linear or branched structure; however, the number of chained atoms is calculated only by the number of atoms forming the longest straight chain. Therefore, in the case where other atoms are, for example, in the case where the chain-forming atom is a carbon atom, the hydrogen atom linked to the carbon atom or the like is not counted in the number of chain atoms. Further, in the case of branching, the number of chained atoms is the number of atoms forming the longest chain. For example, the chain is a n-pentyl group, all of the chain-forming atoms are carbon atoms and the number is five. If the chain is a 2-methylpentyl group, all of the chain-forming atoms are also carbon atoms and the number is 5. The chain-forming atoms can be carbon, oxygen, sulfur or nitrogen, and the appropriate chain-forming atoms can be carbon, oxygen or nitrogen; or carbon or oxygen. The number of chain-forming atoms may be 8 or higher, 9 or higher, 10 or higher, 11 or higher, or 12 or higher. The number of chained atoms may be 30 or lower, 25 or lower, 20 or lower, or 16 or lower.

It was confirmed that the XRD analysis in Equation 1 can be carried out by passing X-rays through the block copolymer sample and then measuring the scattering intensity from the scattering vector. XRD analysis can be performed on block copolymers without any particular pretreatment, and, for example, XRD analysis can be performed by drying the block copolymer under appropriate conditions and then passing X-rays through it. As the X-ray, X-rays having an upright size of 0.023 mm and a horizontal dimension of 0.3 mm may be used. An image of the 2D diffraction pattern scattered from the sample is obtained by using a measuring device (for example, 2D marCCD), and then the resulting diffraction pattern is subjected to the above fitting to obtain a diffraction vector, FWHM, and the like.

The fitting of the diffraction pattern can be performed by numerical analysis of the results of the XRD analysis using the least squares technique. In the above method, about The peak profile in the XRD pattern is taken as the baseline with the lowest intensity position of the XRD diffraction pattern and the lowest intensity is converted to 0. In this state, Gaussian fitting is performed, and then the scattering vector (q) is obtained from the Gaussian fitting result. FWHM. The R square of the Gaussian fit is at least 0.9 or higher, 0.92 or higher, 0.94 or higher, or 0.96 or higher. Methods for obtaining the above information from XRD analysis are known, and, for example, a numerical analysis program (such as origin) can be used.

Scattering substituting values into equation 1 may be 0.5 nm in the range of ¹ to 10 nm scatter values of ^-1. In another embodiment, values are substituted in Equation 1 of the scatter values may be 0.5 nm in the range of ¹ to 10 nm scatter values of ^-1. In another embodiment, the scattering value substituted with the value of Equation 1 may be 0.7 nm ^-1 or higher, 0.9 nm ^-1 or higher, 1.1 nm ^-1 or higher, 1.3 nm. ^-1 or higher, or 1.5 nm ^-1 or higher. In another embodiment, values are substituted in Equation 1 of the scatter values may be ¹ or less 9 nm, 8 nm ^-1 or less, ¹ or less 7 nm, 6 nm ^{- 1} or lower, 5 nm ^-1 or lower, 4 nm ^-1 or lower, 3.5 nm ^-1 or lower, or 3 nm ^-1 or lower.

Equation 1 may represent the relationship between the number of chain-forming atoms and the distance (D) between the blocks including the chain in the case where the block copolymer self-assembles and forms a phase-separated structure. If the number of chain-forming atoms of the block copolymer including the chain conforms to Equation 1, the crystallinity exhibited by the chain is improved, and thus, the phase separation property and the upright alignment property can be greatly improved. In another specific embodiment, nq/(2×π) in Equation 1 may be 4.5 nm ^-1 or lower. Among them, the distance (D, unit, nanometer) between the blocks including the chain can be calculated by the formula D = 2 × π / q. Wherein "D" is the distance between blocks (D, unit: nanometer), and π and q are as defined in Equation 1.

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

For example, a side block is included in the first block or the second block of the block copolymer satisfying the above parameters. Hereinafter, for convenience of explanation, a block including a side chain is referred to as a first block.

In another embodiment, one or both of the first block and the second block of the block copolymer satisfying the above parameters comprise at least an aromatic structure. Both the first block and the second block may comprise an aromatic structure and, in this case, the aromatic structure of the first block may be the same as or different from the aromatic structure of 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 of the halogen atoms described below, and the side chain or at least one halogen The atom can be substituted by an aromatic structure. This block copolymer may comprise two or more blocks.

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

As used herein, "aromatic structure" means an aryl or aryl group and may refer to a monovalent or divalent substituent derived from a compound comprising a benzene ring structure, or at least two benzene rings shared by one or two A carbon atom or a structure linked by any linker, or a derivative of this compound. Unless otherwise It is defined that the aryl or 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. Examples of the aryl or aryl group may be a monovalent or divalent substituent derived from benzene, naphthalene, azobenzene, anthracene, phenanthrene, fused tetraphenyl, anthracene, benzofluorene or the like.

The aromatic structure may be a structure included in the main chain of the block or may be a structure in which a main chain linked to the block is a side chain. For example, suitable adjustments to the aromatic structure that can be included in each block can be used to control the parameters.

For example, to control the parameters, a chain having 8 or more chain-forming atoms can be linked as a side chain to the first block of the block copolymer. In this document, "sidechain" and "chain" may refer to the same subject. Where the first block comprises an aromatic structure, the chain may be linked to an aromatic structure.

The side chain can be a chain linked to the polymer backbone. As stated, the side chain can be a chain comprising 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more chain-forming atoms. The number of chained atoms can be 30 or less, 25 or less, 20 or less, or 16 or less. The chain-forming atoms 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 of the hydrocarbon chain may be substituted with a sulfur atom, an oxygen atom or a nitrogen atom.

Where the side chain is linked to an aromatic structure, the chain may be linked directly to the aromatic structure or may be linked to the aromatic structure via a linker. The linking agent 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)-. Wherein R ₁ is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, wherein X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ - And an alkyl group, an alkenyl group or an alkynyl group, and R ₂ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group. A suitable linker can be an oxygen atom. The side chains can be linked to the aromatic structure via, for example, an oxygen atom or nitrogen.

Where the aromatic structure is linked to the backbone of the block as a side chain, the aromatic structure may also be linked directly to the backbone or may be linked to the backbone via a linker. Examples of the linker may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ or -X ₁ - C(=O)-. Wherein 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 agent for linking 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 of 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, 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. Blocks comprising an aromatic structure comprising a halogen atom can effectively form a phase separation structure by appropriate interaction with other blocks.

An example of the aromatic structure including a halogen atom may be an aromatic structure having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms, but is not limited thereto.

In order to achieve proper phase separation, in the case where both the first and second blocks comprise an aromatic structure, the first block may comprise an aromatic structure not comprising a halogen atom and the second block may comprise a halogen containing The aromatic structure of an atom. Additionally, the aromatic structure of the first block can include direct or via oxygen including Or a linker of a nitrogen atom is linked to the first block of the side chain.

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

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenyl group, and a stretching group. Alkynyl, -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, an alkylene group A radical or an alkynyl group, and Y is a monovalent substituent comprising a cyclic structure having a chain linkage of 8 or more chain-forming atoms.

As used herein, "single bond" refers to the absence of an atom at a relevant position. For example, if X in Formula 1 is a single bond, a structure in which Y is directly linked to a polymer chain can be achieved.

"Alkyl" as used herein, unless otherwise defined, refers to a straight, branched or cyclic alkyl group having from 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. 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 a carbon atom in the alkyl group. The number can be 30 or less, 25 or less, 20 or less, or 16 or less.

"Alkenyl or alkynyl" as used herein, unless otherwise defined, refers to a straight, branched or cyclic olefin having from 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Or an alkynyl group, this alkenyl or alkynyl group may be optionally substituted with at least one substituent. Where the side chain is an alkenyl or alkynyl group, the alkenyl or alkynyl group may comprise 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.

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

"Alkenyl or alkynyl" as used herein, unless otherwise defined, refers to an alkenyl or alkynyl group having from 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. . The alkenyl group or the 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. Wherein 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 carbon atoms. This chain can be linked directly to the aromatic structure or linked to the aromatic structure via the aforementioned linker.

In another embodiment, the first block can be represented by the following 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 It may be an oxygen atom, and Z is a chain having 8 or more chain-forming atoms.

In another embodiment of Formula 2, P can be a pendant phenyl group. Further, Z may 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 phenyl group, Q may be linked 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 case where the block copolymer contains a block containing an aromatic structure including a halogen atom, this block may be a block represented by the following formula 3.

[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 An aryl group of at least one 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. This 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, X ₂ 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 comprise only the two blocks described above or may comprise one or both of the foregoing two blocks and another block.

The method of producing the block copolymer is not particularly limited. For example, block copolymers can be made by living free radical polymerization (LRP). For example, a method such as an anionic polymerization in which a block copolymer is synthesized in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt, which uses organic a 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 in the presence of an organoaluminum compound, which uses an organic alkali metal compound as a polymerization initiator; Base polymerization (ATRP), which uses an atom transfer radical polymerization agent as a polymerization control agent; polymerization is carried out by an electron transfer (ATGET) ATRP-generated activator, which is used in the presence of an electron-generating organic or inorganic reducing agent. An atom transfer radical polymerization agent as a polymerization control agent; an initiator for continuous activator regeneration (ICAR) ATRP; a reversible addition-open chain transfer (RAFT) polymerization reaction using a reductive addition of an inorganic reducing agent - A ring-opening chain transfer agent; and a method of using an organic hydrazine compound as an initiator, a suitable method may be selected from the above methods.

In a specific embodiment, the method of producing a block copolymer may comprise polymerizing a material comprising a monomer capable of forming a block by a living radical polymerization reaction in the presence of a radical initiator and a living polymerization agent. . The method of producing a block copolymer may further comprise precipitating a polymerization product obtained by the foregoing method in a non-solvent.

The polymerization efficiency can be considered, and the kind of the radical initiator is appropriately selected without particular limitation, and an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-(2) can be used. , 4-dimethylvaleronitrile) or a peroxide compound (such as benzamidine peroxide (BPO) or di-tertiary butyl peroxide (DTBP)).

LRP can be used in solvents (such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, digan Dimethyl ether (diglyme), dimethyl It is carried out in carbamide, dimethyl hydrazine or dimethyl acetamide.

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-gum) can be used without limitation. Alkane or petroleum ether).

The aforementioned block copolymers can exhibit excellent phase separation and self-assembly and are also excellent in upright alignment properties. The inventors have confirmed that the above properties can be further improved if the block copolymer further satisfies at least one of the parameters described below.

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

The so-called "in-plane phase diffraction pattern of grazing incidence small-angle X-ray scattering (GISAXS)" means that a peak perpendicular to the X coordinate is observed in the GISAXS diffraction pattern when performing GISAXS analysis. This peak can be confirmed by the upright alignment property of the block copolymer. Therefore, the block copolymer exhibits an in-phase phase diffraction pattern showing an upright alignment property. Further, if the above peaks are observed at regular intervals, the phase separation efficiency can be further improved.

As used herein, "upright" is a vocabulary that takes into account errors, for example, it may include errors of ±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 upright alignment properties on various surfaces that are not subjected to any induced upright alignment treatment. "hydrophobic" used in the text "surface" means a surface having a wetting angle of pure water ranging from 5 to 20 degrees. Examples of the hydrophobic surface may include a polyfluorinated surface treated with a piranha solution, sulfuric acid, or an oxygen plasma, but not The term "hydrophilic surface" as used herein refers to a surface having a wetting angle of pure water ranging from 50 degrees to 70 degrees. Examples of hydrophilic surfaces may include a hydrogen fluoride-treated polyfluorene surface, hexamethyldioxane Treatment of polyfluorene oxide or oxygen plasma treated polydimethyl siloxane, but not limited to this.

Unless otherwise stated, in this document, properties such as wetting angle will vary with the temperature measured at room temperature. As used herein, "room temperature" refers to the temperature in the natural state of being unheated and cooled and may refer to a temperature in the range of from about 10 ° C to 30 ° C, or from about 25 ° C to about 23 ° C.

The layer formed on the hydrophobic or hydrophilic surface and showing the in-plane phase diffraction pattern on the GISAXS may be a layer that is thermally warmed back. In a specific embodiment, the layer for determining GISAXS is, for example, a coating liquid prepared by diluting a block copolymer in a solvent (for example, fluorobenzene) to a concentration of about 0.7% by weight. The coating was made on a corresponding hydrophobic or hydrophilic surface such that the coating had a thickness of about 25 nm and an area of about 2.25 cm ² (width: 1.5 cm, length: 1.5 cm) and then subjected to thermal rewarming treatment. This thermal rewarming can be carried out by maintaining the layer at a temperature of 160 ° C for about 1 hour. GISAXS can be carried out by irradiating the layer prepared above by X-rays such that the incident angle thereof is in the range of 0.12 to 0.23 degrees. A diffraction pattern can be obtained from the diffraction of the layer by a conventional measuring device (for example, 2D marCCD). A technique for confirming the existence of an in-plane phase diffraction pattern from the diffraction pattern obtained above is known in the art.

The block copolymer having the above peaks in GISAXS exhibits excellent self-assembly and can effectively control this property according to the purpose.

In another embodiment, at the time of XRD (X-ray diffraction) analysis, at least one peak appears in the block copolymer within a predetermined range of the scattering vector (q value).

For example, in the XRD analysis, the block copolymer in the scattering vector (q value) of ¹ to 10 nm 0.5 nm ^-1, at least one peak. In other embodiments, the scattering vector (q value) of at least one peak is observed to be in the range of 0.7 nm ^-1 or higher, 0.9 nm ^-1 or higher, 1.1 nm ^-1 or higher, 1.3 nm. ^-1 or higher, or 1.5 nm ^-1 or higher. In other embodiments, the scattering vector (q value) of at least one peak is observed to be in the range of 9 nm ^-1 or lower, 8 nm ^-1 or lower, 7 nm ^-1 or lower, 6 nm. ^-1 or lower, 5 nm ^-1 or lower, 4 nm ^-1 or lower, 3.5 nm ^-1 or lower, or 3 nm ^-1 or lower.

The FWHM (full width at half maximum) of the peak observed in the above range of the scattering vector (q) may be from 0.2 nm ^-1 to 0.9 nm ^-1 . In another embodiment, the FWHM can be 0.25 nm ^-1 or higher, 0.3 nm ^-1 or higher, or 0.4 nm ^-1 or higher. This FWHM can be, in another embodiment, 0.85 nm ^-1 or lower, 0.8 nm ^-1 or lower, or 0.75 nm ^-1 or lower.

As used herein, "FWHM" refers to the width of the peak (the difference between the scattering vectors (q)) at a position where the intensity is half of the maximum intensity. The method for determining the FWHM is as described above.

The peak of the above FWHM appears in the range of the above scattering vector (q) The block copolymer may comprise a crystalline portion suitable for self-assembly. A block copolymer having a peak of the above FWHM in the range of the above scattering vector (q) can exhibit excellent self-assembly.

The method of performing XRD analysis confirmed the above parameters as described above.

In a specific embodiment of the present application, the absolute value of the difference between the surface energies of the first and second blocks may be 10 mN/m or less, 9 mN/m or less, 8 mN/m or less, 7.5. mN/m or lower, or 7 mN/m or lower. The absolute value of the difference between the surface energies may be 1.5 mN/m or higher, 2 mN/m or higher, or 2.5 mN/m or higher. The structure in which the absolute value of the difference between the surface energies between the blocks in the above range is linked by the covalent bond in the above range can achieve effective microphase separation by phase separation due to appropriate non-compatibility. Wherein the first block may be a block having the chain described above.

The surface energy was measured by using a droplet shape analyzer (DSA100 product, manufactured by KRUSS, Co.). Specifically, a coating liquid prepared by diluting a sample (block copolymer or homopolymer) to be measured in fluorobenzene to a solid content of about 2% by weight can be measured on a substrate, so that The coating layer has a thickness of 50 nm and a coating area of 4 cm ² (width: 2 cm, length: 2 cm); the coating is dried at room temperature for about 1 hour; then heated back at 160 ° C for about 1 hour. The surface energy of the layer. After the layer was thermally warmed back, deionized water of known surface tension was dropped and the contact angle was measured thereafter. The above method for obtaining the contact angle of deionized water was repeated five times, and the average value of the obtained contact angles was calculated five times. Incidentally, on the layer which has been subjected to the heat reheating treatment, diiodomethane whose surface tension is known is dropped on the layer and the contact angle is measured thereafter. The above method for obtaining the contact angle of diiodomethane was repeated five times, and the average value of the obtained contact angles was calculated five times. Thereafter, the surface energy was obtained by substituting the value (Strom value) regarding the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angle of deionized water and diiodotoluene. The surface energy of each block in the block copolymer can be obtained by using the above method to obtain a homopolymer obtained by forming a monomer of the corresponding block.

In the case where the block copolymer contains the above chain, the block containing the chain has a surface energy greater than the other blocks. For example, if the first block comprises the chain, the first block has a surface energy greater than the second block. In this case, the surface energy of the first block is in the range of from about 20 mN/m to about 40 mN/m. In another embodiment, the surface energy of the first block can be about 22 mN/m or higher, about 24 mN/m or higher, about 26 mN/m or higher, or about 28 mN/m or higher. The surface energy of the first block can be about 38 mN/m or less, about 36 mN/m or less, about 34 mN/m or less, or about 32 mN/m or less. The block copolymer comprising the above first block and exhibiting the above difference in surface energy above the block can exhibit excellent self-assembly.

In the block copolymer, the difference between the densities of the first and second blocks may be 0.25 g/cm ³ or higher, 0.3 g/cm ³ or higher, 0.35 g/cm ³ or higher. 0.4 g/cm ³ or higher, or 0.45 g/cm ³ or higher. The absolute value of the 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/cm. ³ or lower. The structure in which the absolute value of the difference between the density of the blocks in the above range is linked by the covalent bond in the above range can achieve effective microphase separation by phase separation due to appropriate non-compatibility.

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

In the case where the block copolymer contains the above chain, the density of the block containing the chain is lower than that of the other blocks. For example, if the first block comprises the chain, the density of the first block is lower than the second block. In this case, the density of the first block may range from about 0.9 g/cm ³ to about 1.5 g/cm ³ . In another embodiment, the first block may have a density of about 0.95 g/cm ³ or higher. The first block may have a density of about 1.4 g/cm ³ or less, about 1.3 g/cm ³ or less, about 1.2 g/cm ³ or less, about 1.1 g/cm ³ or less, or about 1.05 g/cm ³ or less. The block copolymer comprising the above first block and exhibiting the above difference between the densities of the blocks can exhibit excellent self-assembly. Surface energy and density were determined 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 the chain, the block having the chain has a volume fraction of 0.4 to 0.8. For example, the first block comprises the chain, the first block has a volume fraction of 0.4 to 0.8 and the second block has a volume fraction of 0.2 to 0.6. The sum of the volume fractions of the first and second blocks is 1. The block copolymer including each block having the above volume fraction exhibits excellent self-assembly. The volume fraction of each block of the block copolymer can be worn by using the density of each block and by gel The molecular weight obtained by the permeation chromatography (GPC) was obtained.

The block copolymer may have, for example, a number average molecular weight (Mn) in the range of from about 3,000 to 300,000. As used herein, "number average molecular weight" refers to the conversion value as determined by GPC (gel permeation chromatography) relative to polystyrene standards. As used herein, unless otherwise indicated, "molecular weight" as used herein refers to a number average molecular weight. In another specific embodiment, the molecular weight (Mn) may be, for example, 3000 or higher, 5000 or higher, 7000 or higher, 9000 or higher, 11,000 or higher, 13,000 or higher, or 15,000 or more. high. 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 more. Low, 90,000 or lower, 80,000 or lower, 70,000 or lower, 60,000 or lower, 50,000 or lower, 40,000 or lower, 30,000 or lower, or 25,000 or lower. The block copolymer may have a polydispersity (Mw/Mn) in the range of 1.01 to 1.60. In another embodiment, the polydispersity can be about 1.1 or higher, about 1.2 or higher, about 1.3 or higher, or about 1.4 or higher.

In the above range, the block copolymer exhibits appropriate self-assembly. The target self-assembled structure can be considered to control the number average molecular weight of the block copolymer and the like.

If the block copolymer comprises at least the first and second blocks, the ratio of the first block (eg, the block comprising the chain) in the block copolymer may range from 10 mol% to 90 mol% Inside.

This application relates to polymers comprising block copolymers Floor. This polymer layer can be used in a variety of applications. For example, it can be used for a biometric device, a recording medium (such as a flash memory), a magnetic memory medium or a pattern forming method, or a power device or an electronic device.

In one embodiment, the block copolymer in the polymer layer can be made into a periodic structure from a self-assembly, including a sphere, a cylinder, a spiral tetrahedron, or a laminate. For example, in a segment of a block copolymer linked to a first block or a second block or other block of the above block via a covalent bond, the other segments may form a regular structure, such as a laminate form, a circle Tube form, etc. The above structure can be arranged upright.

The polymer layer can exhibit an in-plane phase diffraction pattern, i.e., a peak perpendicular to the X coordinate in the GISAXS diffraction pattern of the GISAXS analysis. In a further embodiment, two or more peaks are observed in the X coordinate of the GISAXS diffraction pattern. In the case where two or more peaks were observed, it was confirmed that the scattering vector (q value) has a constant ratio.

This application is also directed to a method of forming a polymer layer using a block copolymer. The method includes forming a polymer layer comprising a block copolymer in a self-assembled state on a substrate. For example, the method comprises forming a layer of a block copolymer or coating a coating liquid (wherein the block copolymer is diluted on a suitable solvent) onto a substrate, and then aging or heat treating the layer, if necessary. .

This aging or heat treatment can be performed 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 heat treatment time is not particularly limited, and the heat treatment may be performed for about 1 minute to 72 hours, but may be caused by Need to change. Further, the heat treatment temperature 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.

This application is also directed to a method of forming a pattern. The method includes selectively removing a first or second block in a block copolymer from a laminate comprising a substrate and a polymer layer formed on the substrate and comprising a self-assembled block copolymer. This 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 in the block copolymer (which is a polymer layer); and etching the substrate thereafter. By the above method, for example, a micro-pattern of a nanometer size can be formed. Further, depending on the shape of the block copolymer in the polymer layer, various shapes of patterns (such as nano-sticks or nanopores) can be formed by the above method. If desired, to form a pattern, the block copolymer can be mixed with another copolymer or homopolymer. The kind of the substrate to which the method is applied can be selected without particular limitation, and, for example, cerium oxide or the like can be applied.

For example, according to this method, a nano-size pattern having a high aspect ratio of cerium oxide can be formed. For example, by forming a polymer layer on ruthenium oxide, selectively removing any block of the block copolymer in a state in which the block copolymer in the polymer layer is formed in a predetermined structure, and in various methods Etching of yttrium oxide (e.g., reactive ion etching) can form various types of patterns (e.g., nano-stick or nanopore patterns). Further, according to the above method, a nano pattern having a high aspect ratio can be formed.

For example, the formed pattern size can be several tens of nanometers, and this Patterns can be used for a variety of purposes, including next-generation information electronic magnetic recording media.

For example, by the above method, a nanostructure pattern (for example, a nanowire) having a width of about 3 to 40 nm placed at intervals of about 6 to 80 nm can be formed. In another embodiment, for example, a nanopore structure having a diameter of about 3 to 40 nm and arranged at intervals of about 6 to 80 nm can be obtained.

Further, in this structure, a nanowire or a nanopore having a high aspect ratio can be formed.

In this method, a method of selectively removing any of the blocks in the block copolymer is not particularly limited, and for example, it is possible to use a suitable electromagnetic wave (for example, ultra-ultraviolet rays) to irradiate the polymer layer to remove the relatively soft embedded layer. The method of paragraph. In this case, the conditions for the ultra-ultraviolet rays may be determined according to the block type of the block copolymer, and the ultra-ultraviolet rays having a wavelength of about 254 nm may be irradiated for 1 to 60 minutes.

In addition, after the ultra-ultraviolet radiation, the polymer layer is acid treated to further remove the segments destroyed by the ultra-ultraviolet rays.

In addition, etching is performed on a substrate using a polymer layer from which the block is selectively removed, which can be performed by reactive ion etching using CF ₄ /Ar ions, and further oxygen can be taken after the above method The plasma treatment removes the polymer layer from the substrate.

The present application can provide block copolymers which have excellent self-assembly and phase separation and are therefore effective for various applications. The application of the block copolymer can also be provided in the present application.

Figures 1 to 6 show SEM images of the polymer layer.

Figures 7 and 8 show the GISAXS diffraction pattern.

Figures 9 through 11 show SEM images of the polymer layer.

Figures 12 through 14 show the GISXAS diffraction pattern.

Hereinafter, the present application will be described in detail with reference to the examples and comparative examples, but the scope of the present application is not limited to the following examples.

NMR analysis

NMR analysis was carried out at room temperature by using an NMR spectrometer comprising a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The sample to be analyzed was diluted in a solvent (CDCl ₃ ) for NMR analysis to a concentration of about 10 mg/ml, and analyzed, and the chemical shift (δ) is represented by Ppm.

<abbreviation>

Br=broad signal, s=single peak, d=doublet, dd=two doublet, t=triplet, dt=two triplet, q=quadruple, p=fivet, m= Multiple peak

2. GPC (gel penetration chromatography)

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

<GPC measurement conditions>

Device: Agilent technologies, Co.'s 1200 Series

Column: Two of PLgel mixed B using Polymer laboratories, Co.

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1mg/mL, injection 200L

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

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

GISAXS analysis was performed in the 3C beam line of Pohang Light Source. The block copolymer to be evaluated was dissolved in fluorobenzene so that the solid content was 0.7% by weight to prepare a coating liquid which was spin-coated on the substrate to have a thickness of about 5 nm. The coating area was controlled to be about 2.25 cm ² (coating area: width = 1.5 cm, length = 1.5 cm). The coating was dried at room temperature for about 1 hour and then subjected to a heat back temperature treatment at about 160 ° C for about 1 hour to effect a phase separation structure. Thus, a layer of phase separated structure is formed. The formed layer is irradiated with X-rays such that the incident light is from about 0.12 degrees to 0.23 degrees, which corresponds to an angle between the critical angle of the layer and the critical angle of the substrate, and then is scattered from the layer by using a 2D marCCD. X-ray diffraction pattern. At this time, the distance from the layer to the detector is selected such that the self-assembly pattern in the layer can be effectively observed in the range of about 2 m to 3 m. As the substrate, it may be a substrate having a hydrophilic surface (a ruthenium substrate treated with a samarium ruthenium solution, a wet angle of about 5 degrees with respect to pure water at room temperature) or a substrate having a hydrophobic surface (a ruthenium substrate, which is subjected to HMDS ( Hexamethyldioxane treatment, about 60 degrees of wetting angle with pure water at room temperature).

4. XRD analysis

The XRD pattern was identified by passing X-rays through a sample in the 4C beam line of Pohang Light Source, measuring the scattering intensity from the scattering vector (q). A powder obtained by using a block copolymer without any specific pretreatment was purified to remove impurities from the sample as a sample, which was placed in a tank for measuring XRD. During the XRD pattern analysis, as the X-rays, X-rays having an upright size of 0.023 mm and a horizontal size of 0.3 mm were used, and a measuring device (for example, 2D marCCD) was used as a detector. The 2D diffraction pattern scattered from the sample is an image. Using numerical analysis, using the least squares technique, the obtained diffraction pattern is analyzed to obtain information (such as scattering vector and FWHM). This analysis is performed by the origin program. The XRD diffraction pattern has the position of the lowest intensity as the baseline and the lowest intensity is converted to 0, after which the Gaussian fitting is performed on the contour of the peak in the XRD pattern, and then the scattering vector (q) and FWHM are obtained from the Gaussian fitting. The R square of the Gaussian fit is set to 0.96 or higher.

5. Determination of surface energy

The surface energy was measured by using a droplet shape analyzer (DSA100 product, manufactured by KRUSS, Co.). It was evaluated that the coating liquid (by dissolving the material to be evaluated in fluorobenzene so that the solid content was 2% by weight) was spin-coated on the tantalum wafer so that the coating layer had a thickness of 50 nm (coating area: Width = 2 cm, length = 2 cm); the coating was dried at room temperature for about 1 hour; then the surface energy of the polymer layer was formed by heat-recovering at 160 ° C for about 1 hour. After the thermal rewarming, deionized water droplets whose surface tension is known were placed on the layer, and then the contact angle was obtained, repeated 5 times, and the average value of the obtained 5 contact angles was calculated. After the layer was warmed back to the temperature, diiodomethane having a known surface tension was dropped thereon, and then a contact angle was obtained, which was repeated 5 times, and the average value of the obtained 5 contact angles was calculated. The surface energy can be obtained by the Owens-Wendt-Rabel-Kaelble method by using the average value obtained by the contact angle of deionized water and diiodotoluene, and by substituting the value of the surface tension of the solvent (Strom value). The surface energy of each block in the block copolymer can be obtained by using the above method to form a homopolymer obtained by forming a monomer corresponding to the block.

6. Determination of volume fraction

The volume fraction of each block of the block copolymer was calculated based on the molecular weight measured by GPC (gel permeation chromatography) and the density at room temperature. Among them, the density is determined by the buoyancy method, specifically, by the mass of the solvent determined in the solvent (ethanol, known in mass and density).

Preparation Example 1. Synthesis of Monomer (A)

The following compound of the formula A (DPM-C12) was synthesized by the following method. In a 250 mL bottle, hydroquinone (10.0 g, 94.2 mmole) and 1-bromodecane (23.5 g, 94.2 mmole) were added and dissolved in 100 mL of acetonitrile, and an excess of potassium carbonate was added thereto. The mixture was at 75 ° C in nitrogen. The reaction was carried out for about 48 hours. After the reaction, the remaining potassium carbonate and the acetonitrile used in the reaction were removed. Treatment with a mixed solvent of dichloromethane (DCM) and water was carried out, and the separated organic layer was collected and dried over MgSO ₄ . Thereafter, using DCM, via column chromatography, a white solid intermediate was obtained with a yield of about 37%.

<Results of NMR analysis of intermediate products>

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)

Synthetic intermediate (9.8 g, 35.2 mmole), methacrylic acid (6.0 g, 69.7 mmole), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmole) and p-dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmole) was placed in a bottle, 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 obtained in the reaction was removed by a filter, and the remaining dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as a mobile phase, and the obtained product was recrystallized from a mixed solvent of methanol and water (mixed in a 1:1 weight ratio), thereby obtaining a white solid. Product (DPM-C12) (7.7 g, 22.2 mmole), yield 63%.

<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); δ 1.34-1.27 (m, 16H); δ 0.88 (t, 3H)

Wherein 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 Example 1, except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR Results of DPM-C4>

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 3.95 (t) , 2H); δ2.06 (dd, 3H); δ 1.76 (p, 2H); δ 1.49 (p, 2H); δ 0.98 (t, 3H)

Wherein 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 Example 1 except that 1-bromooctane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR 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); δ 1.33-1.29 (m, 8H); δ 0.98 (t, 3H)

Wherein R is a linear alkyl group having 8 carbon atoms.

Preparation Example 4. Synthesis of Monomer (C)

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

<NMR 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); δ 1.34-1.28 (m, 12H); δ 0.89 (t, 3H)

Wherein R is a linear alkyl group having 10 carbon atoms.

Preparation Example 5. Synthesis of Monomer (D)

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

<NMR 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); δ1.36-1.27 (m, 20H); δ 0.88 (t, 3H)

Wherein R is a linear alkyl group having 14 carbon atoms.

Preparation Example 6. Synthesis of Monomer (E)

The compound of the following formula E was synthesized according to the method of Preparation Example 1 except that 1-bromohexadecane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR 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); δ1.36-1.26 (m, 24H); δ 0.89 (t, 3H)

[Formula E]

Wherein 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 split-chain transfer) reagent (cyanoisopropyl benzoate), 23 mg of AIBN (azobisisobutyronitrile) and 5.34 mL Benzene was added to a 10 mL bottle, followed by stirring at room temperature for 30 minutes, followed by 4 hours of RAFT (reversible addition split-chain transfer) polymerization at 70 °C. After the polymerization, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to give a pink macroinitiator. The yield of this macroinitiator was about 86%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 9,000 and 1.16, respectively.

0.3 g of macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mL of benzene were added to a 10 mL Schlenk bottle, followed by stirring at room temperature for 30 minutes, followed by RAFT (reversible addition split-chain transfer) polymerization at 115 ° C for 4 hours. reaction. After the polymerization, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to give a pale pink block copolymer. The yield of this block copolymer was about 18%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 16,300 and 1.13, respectively. This 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 by the same method as in Example 1, except that the macroinitiator prepared in the monomer (B) of Preparation Example 3 was used instead of the monomer (A) of Preparation Example 3, and pentafluorostyrene was used. This block copolymer includes a first block derived from the monomer (B) of Preparation Example 1 and a second block derived from pentafluorostyrene.

Example 3

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

Example 4

The block copolymer was prepared by the same method as in Example 1, except that the macroinitiator prepared by using the monomer (D) of Preparation Example 5 was used instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. This 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 by the same method as in Example 1, except that the macroinitiator prepared in the monomer (E) of Preparation Example 6 was used instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. This 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

A block copolymer was obtained in the same manner as in Example 1, except that the monomer (G) of Preparation Example 2 was used instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. This 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

A block copolymer was obtained in the same manner as in Example 1, except that 4-methoxyphenyl methacrylate was used instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. This block copolymer comprises a first block derived from 4-methoxyphenyl methacrylate and a second block derived from pentafluorostyrene.

Comparative example 3

A block copolymer was obtained in the same manner as in Example 1, except that dodecyl methacrylate was used instead of the monomer (A) of Preparation Example 1 and pentafluorostyrene was used. This block copolymer comprises a first block derived from dodecyl methacrylate and a second block derived from pentafluorostyrene.

The GPC results for the macroinitiator and the example block copolymer are shown in Table 1.

Test Example 1. XRD Analysis

According to the above method, XRD analysis result of the block copolymer shown in the following Table 2 (in the case of Comparative Example 3, a peak was not observed in the scattering vector range of 0.5 nm ^-1 to 10 ^-1 nm).

Test Example 2: Self-assembly measurement

A coating liquid having a solid content of about 0.7% by weight prepared by dissolving the block copolymer of the example or the comparative example in fluorobenzene is spin-coated on the tantalum wafer so that the coating thickness is 5 nm (coating) Covering area: width x length = 1.5 cm x 1.5 cm), and drying at room temperature for 1 hour, followed by heat returning at about 160 ° C for 1 hour to obtain a self-assembled polymer layer. Thereafter, an SEM (Scanning Electron Microscope) image of the formed polymer layer was obtained. 1 to 5 are the results of Examples 1 to 5, respectively. As evidenced by the figure, in the case of the block copolymer of the example, a self-assembled polymer layer having a line pattern was efficiently formed. However, the comparative example did not achieve proper phase separation. 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: GISAXS diffraction pattern confirmation

Figure 7 shows the block copolymer of Example 1 and pure water in the chamber. The results of the GISAXS (grazing incidence small-angle X-ray scattering) analysis of the hydrophilic surface with a temperature of about 5 degrees of hydrophilic contact angle, FIG. 8 shows that the block copolymer of Example 1 has a contact angle with pure water at room temperature of about 60 degrees. The results of the surface GISAXS (grazing incidence small angle X-ray scattering) analysis. From Figs. 7 and 8, it was confirmed that the in-plane phase diffraction pattern was observed in any case. Among them, it was confirmed that the block copolymer can exhibit an upright alignment property on various substrates.

Further, by using the block copolymer of Example 1, the polymer layer was formed by the same method as described above.矽 substrate (5 degree contact with pure water at room temperature), yttrium oxide substrate (contact angle with pure water at room temperature of 45 degrees) and HMDS (hexamethyldifluoride) A polymer layer was formed on the azlacane-treated polymethoxyl plate (60 degree contact angle with pure water at room temperature). Figures 9 through 11 are SEM images of the polymer layers on surfaces having contact angles of 5, 45 and 60 degrees, respectively. From the figure, it was confirmed that the block copolymer forms a phase-separated structure irrespective of the surface properties of the substrate.

Test Example 3. Determination of properties of block copolymers

The evaluation results of the respective block copolymers measured by the above methods are shown in the following table.

Test Example 4.

Further, block copolymers having different volume fractions were prepared according to the same method as in Example 1, except that the molar ratio of the monomer and the macroinitiator was controlled.

The volume fraction is as follows.

The volume fraction of each block of the block copolymer was calculated based on the molecular weight measured by GPC (gel penetration chromatography) and the density at room temperature. Among them, the density is determined by the buoyancy method, specifically, it is borrowed in solvent (B The mass of the alcohol (the mass and the density in air is known) and the GPC calculation according to the above method.

The coating liquid prepared by dissolving various block copolymers in fluorobenzene to a solid content of about 0.7% by weight is spin-coated on the tantalum wafer so that the coating has a coating thickness of 5 nm. (Coating area: width = 1.5 cm, length = 1.5 cm) and then drying at room temperature for 1 hour and then subjecting to thermal rewarming treatment at about 160 ° C for 1 hour to obtain a polymer layer. After that, GISAXS was performed, and the results are shown in the figure. 12 to 14 are the results of Samples 1 to 3, respectively, and it was confirmed that the in-phase phase diffraction pattern was observed and the block copolymer had an upright alignment property.

Claims (9)

A block copolymer comprising a first block having a side chain and a number of atoms (n) different from the first block and a chain of the side chain satisfying the second block of the following Equation 1, wherein the One block is represented by the following formula 2, and the second block is represented by the following formula 4: [Equation 1] 3 nm ^-1 to 5 nm ^-1 = nq/(2 x π) wherein "n" is The number of stranded atoms, "q" is the smallest scattering vector in the scattering vector at the peak observed in the X-ray diffraction analysis or the scattering vector at the peak with the largest area observed, and in Equation 1 π is the ratio of the circumference to its diameter: Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, P is an extended aryl group having 6 to 12 carbon atoms, and Q is an oxygen atom, Z Is a chain having a chain forming atom, wherein the chain forming atom is carbon, oxygen, sulfur or nitrogen, and the number of atoms forming the chain therein is 8 to 20; Wherein X ₂ is a single bond or an alkylene group having 1 to 20 carbon atoms, and R ₁ to R ₅ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, and have 1 to 20 carbons. The number of haloalkyl or halogen atoms of the atom, and the halogen atom included in R ₁ to R ₅ thereof is 1 or more. The patentable scope of application of the block copolymer of item 1, wherein the Equation 1 of the scattering vector system 1 nm to 3 nm ^{-1 -1.} The block copolymer of claim 1, wherein the first block has a volume fraction of 0.4 to 0.8, the second block has a volume fraction of 0.2 to 0.6, and the first and the second The volume fraction of the block is 1. The block copolymer of claim 1, wherein the number average molecular weight is from 3,000 to 300,000. The block copolymer of claim 1, 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 application. The polymer layer of claim 6 wherein the in-plane phase diffraction pattern is exhibited in grazing incidence small angle X-ray scattering. 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 application. A method of forming a pattern comprising selectively removing a block copolymer from a substrate comprising a polymer layer comprising a substrate and a self-assembled product formed on the substrate and comprising the block copolymer of claim 1 The first block or the second block.