KR102159495B1 - Block copolymer - Google Patents

Abstract

In the present application, a block copolymer and its use may be provided. The block copolymer of the present application has excellent self-assembly characteristics or phase separation characteristics, and may evenly form a self-assembled structure vertically oriented on a substrate.

Description

Block copolymer {BLOCK COPOLYMER}

This application relates to a block copolymer and its use.

Block copolymers have a molecular structure in which polymer blocks having different chemical structures are connected through covalent bonds. The block copolymer may form a periodically arranged structure such as a sphere, a cylinder, or a lamella by phase separation. The size of the domain of the structure formed by the self-assembly phenomenon of the block copolymer can be widely controlled, and various types of structures can be fabricated. It can be applied to an element, magnetic recording medium, or pattern formation by lithography.

The present application provides a block copolymer and its use.

In the present specification, the term alkyl group may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms unless otherwise specified. The alkyl group may be a linear, branched or cyclic alkyl group, and may be optionally substituted with one or more substituents.

In the present specification, the term alkoxy group may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be a linear, branched or cyclic alkoxy group, and may be optionally substituted with one or more substituents.

In the present specification, the term alkenyl group or alkynyl group refers to an alkenyl group or alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. can do. The alkenyl group or alkynyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the term alkylene group may mean an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkylene group may be a linear, branched or cyclic alkylene group, and may be optionally substituted with one or more substituents.

In the present specification, the term alkenylene group or alkynylene group is an alkenylene group or alkynylene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. It can mean qi. The alkenylene group or alkynylene group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the term aryl group or arylene group, unless otherwise specified, one benzene ring structure, two or more benzene rings are linked while sharing one or two carbon atoms, or linked by an arbitrary linker It may mean a monovalent or divalent moiety derived from a compound or a derivative thereof having a structure to be formed.

Unless otherwise specified, the aryl group or the arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms.

In the present application, the term aromatic structure may mean the aryl group or an arylene group.

In the present specification, the term alicyclic ring structure means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms unless otherwise specified. .

In the present application, the term single bond may mean a case where no separate atom exists at the corresponding site. For example, in the structure indicated by A-B-C, when B is a single bond, it may mean that no separate atom exists at the site indicated by B, and A and C are directly connected to form a structure indicated by A-C.

In the present application, substituents that may be optionally substituted in an alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group, alkoxy group, aryl group, arylene group, straight chain or aromatic structure, etc., include hydroxy group, halogen Atom, carboxyl group, glycidyl group, acryloyl group, methacryloyl group, acryloyl group oxy, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynyl A ren group, an alkoxy group, or an aryl group may be exemplified, but is not limited thereto.

The block copolymer of the present application may include a block (hereinafter, referred to as a first block) having a unit represented by Formula 1 below. The first block may consist of only units represented by the following formula (1), or may include other units in addition to the units of formula (1).

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group, X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, -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 alkenylene group or an alkynylene group, and Y Is a monovalent substituent including a ring structure to which a straight chain having 8 or more chain forming atoms is connected.

In Formula 1, X may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O-, or -OC(=O)-, or -C(=O)-O-, in another example, It is not limited.

In Formula 1, the monovalent substituent of Y includes a chain structure formed of at least 8 chain-forming atoms.

In the present application, the term chain-forming atom means an atom that forms a linear structure of a predetermined chain. The chain may be linear or branched, but the number of chain-forming atoms is calculated only from the number of atoms forming the longest straight chain, and other atoms bonded to the chain-forming atom (for example, the chain-forming atom is In the case of a carbon atom, the hydrogen atom bonded to the carbon atom, etc.) is not counted. In addition, in the case of a branched chain, the number of chain forming atoms may be calculated as the number of chain forming atoms forming the longest chain. For example, when the chain is an n-pentyl group, all of the chain forming atoms are carbon and the number is 5, and even when the chain is a 2-methylpentyl group, all the chain forming atoms are carbon and the number is 5. As the chain-forming atom, carbon, oxygen, sulfur, or nitrogen may be exemplified, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of chain-forming atoms may also be 30 or less, 25 or less, 20 or less, or 16 or less.

The unit of Formula 1 may allow the block copolymer to exhibit excellent self-assembly properties.

In one example, the chain may be a linear hydrocarbon chain such as a linear alkyl group. In this case, the alkyl group may be an alkyl group having 8 or more carbon atoms, 8 to 30 carbon atoms, 8 to 25 carbon atoms, 8 to 20 carbon atoms, or 8 to 16 carbon atoms. At least one of the carbon atoms of the alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted with another substituent.

In Formula 1, Y includes a ring structure, and the chain may be connected to the ring structure. By such a ring structure, the self-assembly property of the block copolymer formed by the monomer may be further improved. The ring structure may be an aromatic structure or an alicyclic structure.

The chain may be directly connected to the ring structure or may be connected via a linker. As the linker, an oxygen atom, a sulfur atom, -NR ₁ -, S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, -C(=O)-X ₁ -or- X ₁ -C(=O)-, etc. may be exemplified, wherein R ₁ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and X ₁ is a single bond, an oxygen atom, a sulfur atom , -NR ₂ -, -S(=O) ₂ -, may be an alkylene group, an alkenylene group or an alkynylene group, wherein R ₂ may be a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group have. An oxygen atom or a nitrogen atom may be exemplified as a suitable linker. The chain may be connected to an aromatic structure via, for example, an oxygen atom or a nitrogen atom. In this case, the linker may be an oxygen atom, or -NR _1- (wherein R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

Y in Formula 1 may be represented by the following Formula 2 in an example.

[Formula 2]

In Formula 2, P is an arylene group, Q is a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is 8 It is the chain having more than one chain forming atom. When Y in Formula 1 is a substituent of Formula 2, P in Formula 2 may be directly linked to X in Formula 1.

As a suitable example of P in Formula 2, an arylene group having 6 to 12 carbon atoms, for example, a phenylene group may be illustrated, but is not limited thereto.

In Formula 2, Q is a suitable example, an oxygen atom or -NR _1- (wherein R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

As a suitable example of the unit of Formula 1, in Formula 1, R is hydrogen or an alkyl group, for example, hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, and Y is the above In Formula 2, P is an arylene group or phenylene having 6 to 12 carbon atoms, Q is an oxygen atom, and Z is a unit of the aforementioned chain having 8 or more chain forming atoms.

Accordingly, a suitable exemplary unit of Formula 1 includes a unit of Formula 3 below.

[Formula 3]

In Formula 3, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, P is an arylene group having 6 to 12 carbon atoms, Q is an oxygen atom, and Z is a chain forming valency It is the chain of 8 or more.

In the block copolymer, the second block included together with the first block including the unit as described above may include at least a unit represented by Formula 5 below.

[Formula 5]

In Formula 5, X ₂ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenylene group, an alkynylene 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 alkenylene group or an alkynylene group, and R ₁ to R ₅ are Each independently hydrogen, an alkyl group, a haloalkyl group, a halogen atom or an alkoxy group, at least one of R ₁ to R ₅ is an alkoxy group, and the number of halogen atoms contained in R ₁ to R ₅ is 1 or more.

In Chemical Formula 5, X ₂ may be a single bond, an oxygen atom, an alkylene group, -C(=O)-O- or -OC(=O)- in another example.

In Formula 5, R ₁ to R ₅ are each independently hydrogen, an alkyl group, a haloalkyl group, or a halogen atom, but R ₁ to R ₅ are 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms , For example, it may contain a fluorine atom. The number of halogen atoms contained in R ₁ to R ₅ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

As the halogen atom included in Chemical Formula 5, a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately used, but is not limited thereto.

The unit of Formula 5 includes at least one alkoxy group as described above, and the alkoxy group may be, for example, located in R ₃ . Due to the presence of the alkoxy group contained in the unit of Formula 5, the difference in surface energy between the first block and the second block can be reduced to express excellent orientation, and since the alkoxy group is located at R ₃ , the block copolymer is While the self-assembled structure exhibits excellent phase separation characteristics, it may be possible to implement a fine pattern having a line width of 8 nm to 15 nm.

The alkoxy group included in Chemical Formula 5 may have 1 or more or 2 or more carbon atoms, and may be 20 or less, 16 or less, 12 or less, 8 or less, or 4 or less. Since the unit of Formula 5 contains an alkoxy group that satisfies the above range, the block copolymer exhibits excellent phase separation characteristics, and at the same time, the vertical orientation of the block copolymer may be induced in a large area in a short time by thermal annealing. .

The second block of the block copolymer may further include other units in addition to the units of Formula 5. In this case, the types of units that can be included are not particularly limited.

For example, the second block is a polyvinylpyrrolidone unit, a polylactic acid unit, a polyvinylpyridine unit, a polystyrene unit such as polystyrene or polytrimethylsilylstyrene, and a polyethylene oxide. A polyalkylene oxide unit such as (polyethylene oxide), a polybutadiene unit, a polyisoprene unit, or a polyolefin unit such as polyethylene may be further included.

The block copolymer of the present application is a block copolymer including at least one of the first and second blocks described above, and is a diblock copolymer including only the two blocks, or at least one of the first and second blocks. It may be a triblock or more block copolymer including two or more, or included together with other blocks.

The block copolymer as described above may basically exhibit excellent phase separation or self-assembly characteristics. Since the block copolymer contains two or more polymer chains linked by covalent bonds, phase separation occurs. The block copolymer of the present application exhibits excellent phase separation properties, and may form a nano-scale structure by microphase separation, if necessary. The shape and size of the nanostructure can be controlled by the size of the block copolymer (molecular weight, etc.) or the relative ratio between blocks. As a structure formed by phase separation, a sphere, a cylinder, a gyroid, a lamella, and an inversion structure may be exemplified, and the ability of the block copolymer to form such a structure may be referred to as self-assembly. The block copolymer of the present application may include the first block and the second block described above so that the block copolymer exhibits vertical orientation. In the present application, the term vertical orientation indicates the orientation of the block copolymer, and the orientation of the nanostructure formed by the block copolymer may mean an orientation perpendicular to the substrate direction. The technology of adjusting the self-assembled structure of the block copolymer horizontally or vertically on various substrates occupies a very large weight in practical application of the block copolymer. In general, the orientation of the nanostructures in the block copolymer film is determined by which blocks of the blocks forming the block copolymer are exposed to the surface or air. In general, since many substrates are polar and air is non-polar, a block having a larger polarity among the blocks of the block copolymer is wetting on the substrate, and a block having a smaller polarity is wetting at the interface with air. ). Therefore, various techniques have been proposed in order to simultaneously wet blocks having different properties of the block copolymer on the substrate side, and the most representative technique is the adjustment of orientation by applying a neutral surface preparation. However, in one aspect of the present application, the block copolymer may be vertically aligned even on a substrate to which a known treatment known to achieve vertical orientation including a neutral surface treatment or the like has not been performed. In addition, in an additional aspect of the present application, the vertical orientation as described above may be induced in a large area within a short time by thermal annealing.

The number average molecular weight (Mn) of the block copolymer may be in the range of 16,500 to 40,000, for example. In this specification, the term number average molecular weight is a value in terms of standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight in the present specification means a number average molecular weight unless otherwise specified. In another example, the molecular weight (Mn) may be, for example, 16,700 or more, 16,900 or more, 17,000 or more, 17,200 or more, 17,400 or more, 17,600 or more, 17,800 or more, or 18,000 or more. In another example, molecular weight (Mn) is 40,000 or less, 39,500 or less, 39,000 or less, 38,500 or less, 38,000 or less, 37,500 or less, 37,000 or less, 36,500 or less, 36,000 or less, 35,500 or less, 35,000 or less, 34,500 or less, 34,000 or less, 33,500 or less Or 33,000 or less. The block copolymer of the present application may exhibit excellent self-assembly characteristics within the above molecular weight range, and may form a vertically oriented self-assembly structure.

The block copolymer may have a polydispersity (Mw/Mn) within the range of 1.01 to 1.60. The degree of dispersion may be about 1.04 or more, about 1.08 or more, about 1.12 or more, or about 1.16 or more in other examples. In this range, the block copolymer may exhibit appropriate self-assembly properties. The number average molecular weight of the block copolymer may be adjusted in consideration of a desired self-assembled structure.

The block copolymer of the present application may include a block having a volume fraction in the range of 0.4 to 0.8, and a block having a volume fraction in the range of 0.2 to 0.6. When the block copolymer includes the chain, the volume fraction of the block having the chain may be in the range of 0.4 to 0.8. For example, when the chain is included in the first block, the volume fraction of the first block may be in the range of 0.4 to 0.8, and the volume fraction of the second block may be in the range of 0.2 to 0.6. The sum of the volume fractions of the first block and the second block may be 1. The block copolymer including each block in the volume fraction as described above may exhibit excellent self-assembly characteristics. The volume fraction of each block of the block copolymer can be calculated based on the density of each block and the molecular weight measured by GPC (Gel Permeation Chromatogrph).

When the block copolymer includes at least the first and second blocks, the proportion of the first block, for example, the block including the chain, in the block copolymer is 10 mol% to 90 mol%. May be within range.

In the present application, a specific method of preparing the block copolymer as described above is not particularly limited as long as it includes the step of forming at least one block of the block copolymer using the monomers capable of forming each unit described above.

For example, the block copolymer can be prepared by using the monomer LRP (Living Radical Polymerization). For example, anionic polymerization synthesized in the presence of an inorganic acid salt such as an alkali metal or alkaline earth metal salt by using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator, or polymerization of an organic alkali metal compound Anionic polymerization method that is used as an initiator and synthesized in the presence of an organic aluminum compound, atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization control agent, and an atom transfer radical polymerization agent as a polymerization control agent, ARGET (Activators Regenerated by Electron Transfer) atom transfer radical polymerization (ATRP), ICAR (Initiators for continuous activator regeneration) atom transfer radical polymerization (ATRP), reversible addition of inorganic reducing agents- There are reversible addition-cleavage chain transfer polymerization method (RAFT) using a cleavage chain transfer agent or a method using an organic tellurium compound as an initiator, and a suitable method may be selected and applied from among these methods.

For example, the block copolymer may be prepared in a manner that includes polymerizing a reactant including monomers capable of forming the block by a living radical polymerization method in the presence of a radical initiator and a living radical polymerization reagent. .

When preparing a block copolymer, a method of forming another block included in the copolymer together with a block formed using the monomer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired block. Blocks can be formed.

The process of preparing the block copolymer may further include, for example, precipitating the polymerization product generated through the above process in a non-solvent.

The type of the radical initiator is not particularly limited, and may be appropriately selected in consideration of polymerization efficiency, for example, AIBN (azobisisobutyronitrile), ABCN (1,1'-Azobis (cyclohexanecarbonitrile)) or 2,2'-azobis- Azo compounds such as 2,4-dimethylvaleronitrile (2,2'-azobis-(2,4-dimethylvaleronitrile)) or peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP) are used. Can be used.

Living radical polymerization process is, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, anisole, tetrahydrofuran, dioxane, monoglyme, diglyme. , Dimethylformamide, dimethylsulfoxide, or dimethylacetamide.

As the non-solvent, for example, alcohols such as methanol, ethanol, normal propanol or isopropanol, glycols such as ethylene glycol, ethers such as n-hexane, cyclohexane, n-heptane or petroleum ether may be used, It is not limited thereto.

The present application also relates to a polymer membrane comprising the block copolymer. The film may be used for various purposes, for example, various electronic or electronic devices, a process of forming the pattern, or a recording medium such as a magnetic storage recording medium, a flash memory, or a biosensor.

In one example, the block copolymer in the polymer membrane may implement a periodic structure including a sphere, a cylinder, a gyroid, or a lamellar through self-assembly. .

For example, in the block copolymer, in the segment of the first or second block or other block covalently bonded thereto, other segments may form a regular structure such as a lamella shape or a cylinder shape.

The present application also relates to a method of forming a polymer film using the block copolymer. The method may include forming a polymer film including the block copolymer on a substrate in a self-assembled state. For example, the method may include forming a layer of the block copolymer or a coating solution diluted in an appropriate solvent on a substrate by coating or the like and, if necessary, aging the layer or heat treatment.

The aging or heat treatment may be performed based on, for example, a phase transition temperature or a glass transition temperature of the block copolymer, and, for example, may be performed at a temperature equal to or higher than the glass transition temperature or the phase transition temperature. The time during which such heat treatment is performed is not particularly limited, and may be performed within a range of, for example, about 1 minute to 72 hours, but this may be changed as necessary. In addition, the heat treatment temperature of the polymer thin film may be, for example, about 100°C to 250°C, but this may be changed in consideration of the block copolymer used.

In another example, the formed layer may be solvent aged for about 1 minute to 72 hours in a non-polar solvent and/or a polar solvent at room temperature.

After forming the polymer film as described above, a process of crosslinking the second block may be additionally performed, and the method of performing this crosslinking process is as described above.

The present application also relates to a pattern forming method. The method includes, for example, selectively removing the first or second block of the block copolymer from a laminate having a substrate and a polymer film formed on the surface of the substrate and including the self-assembled block copolymer May include the process of doing. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film including the block copolymer on a substrate, and etching the substrate after selectively removing one or more blocks of the block copolymer present in the film. . In this way, for example, it is possible to form a fine pattern on a nano scale. In addition, various types of patterns such as nanorods or nanoholes may be formed through the above method according to the shape of the block copolymer in the polymer film. If necessary, the block copolymer and other copolymers or homopolymers may be mixed to form a pattern. The type of the substrate applied to this method is not particularly limited, and may be selected as necessary, and for example, silicon oxide or the like may be applied.

In the polymer film applied in the process of selectively removing the first and/or second blocks, the above-described second block may include a crosslinked structure, and the method of implementing such a crosslinked structure is as described above.

For example, the above method can form a nanoscale pattern of silicon oxide exhibiting a high aspect ratio. For example, after forming the polymer film on silicon oxide and selectively removing one block of the block copolymer while the block copolymer in the polymer film has a predetermined structure, silicon oxide is removed in various ways, for example , Reactive ion etching, etc. may be used to implement various shapes including nanorods or nanohole patterns. In addition, through such a method, it may be possible to implement a nano pattern having a large aspect ratio.

For example, the pattern may be implemented on a scale of several tens of nanometers, and such a pattern may be used in various applications including, for example, a magnetic recording medium for next-generation information and electronic devices.

For example, according to the above method, a nanostructure having a width of about 3 nm to 40 nm, for example, a pattern in which nanowires are disposed at an interval of about 6 nm to 80 nm can be formed. In another example, it is possible to implement a structure in which nanoholes having a width of about 3 nm to 40 nm, for example, a diameter, form a gap of about 6 nm to 80 nm.

In addition, in the above structure, nanowires or nanoholes may have a large aspect ratio.

In the above method, a method of selectively removing any one block of the block copolymer is not particularly limited, and for example, a method of removing relatively soft blocks by irradiating an appropriate electromagnetic wave, for example, ultraviolet rays, etc., to the polymer membrane is employed. Can be used. In this case, the ultraviolet irradiation conditions are determined according to the type of block of the block copolymer, and for example, ultraviolet rays having a wavelength of about 254 nm may be irradiated for 1 to 60 minutes.

In addition, subsequent to ultraviolet irradiation, the polymer film may be treated with an acid or the like to further remove segments decomposed by ultraviolet rays.

In addition, the step of etching the substrate using the polymer film from which the block has been selectively removed as a mask is not particularly limited, and may be performed through, for example, a reactive ion etching step using CF ₄ /Ar ions, etc. Subsequently, the step of removing the polymer film from the substrate by oxygen plasma treatment or the like may also be performed.

In the present application, a block copolymer and its use may be provided. The block copolymer of the present application has excellent self-assembly characteristics or phase separation characteristics, and may evenly form a self-assembled structure vertically oriented on a substrate.

1 is a SEM photograph of a nanostructure in which a 17 nm-class pattern was formed, expressed through heat treatment of the block copolymer of Example 1. FIG.
2 is a SEM photograph of a nanostructure in which a 30 nm-class pattern was formed, which was expressed through heat treatment of the block copolymer of Example 2. FIG.
3 is a SEM photograph of a nanostructure expressed through heat treatment of the block copolymer of Comparative Example 1.

Hereinafter, the present application will be described in more detail through Examples and Comparative Examples according to the present application, but the scope of the present application is not limited by the Examples presented below.

1. NMR measurement

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

<Applicable abbreviation>

br = wide signal, s = singlet, d = doublet, dd = double doublet, t = triplet, dt = double triplet, q = quartet, p = quintet, m = multiplet.

2. GelPermeation Chromatograph (GPC)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). In a 5 mL vial, a material to be analyzed, such as a block copolymer or a macroinitiator of Examples or Comparative Examples, is added, and diluted in tetrahydrofuran (THF) to a concentration of about 1 mg/mL. Then, the standard sample for calibration and the sample to be analyzed were filtered through a filter (syringe filter, pore size: 0.45 µm), and then measured. Agilent technologies' ChemStation was used as the analysis program, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by comparing the elution time of the sample with the calibration curve, and the molecular weight distribution (PDI) was calculated using the ratio (Mw/Mn). ) Was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Instrument: 1200 series from Agilent technologies

Column: Two PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35℃

Sample concentration: 1mg/mL, 200L injection

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

Preparation Example 1.

Preparation Example 1. Synthesis of Monomer (A)

The compound of formula A (DPM-C12) was synthesized in the following manner. Add hydroquinone (10.0g, 94.2 mmol) and 1-Bromododecane (23.5 g, 94.2 mmol) to a 250 mL flask, and dissolve in 100 mL of acetonitrile, Potassium carbonate was added and reacted at 75° C. for about 48 hours under nitrogen conditions. Potassium carbonate remaining after the reaction was removed by filtering, and acetonitrile used in the reaction was also removed. A mixed solvent of dichloromethane (DCM, dichloromethane) and water was added thereto to work up, and the separated organic layer was collected and passed through MgSO ₄ to dehydrate. Then, using dichloromethane (DCM, dichloromethane) in column chromatography to obtain the target product (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as a white solid in a yield of about 37%.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): ?6.77 (dd, 4H); ?4.45(s, 1H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p, 2H); δ 1.33-1.26 (m, 16H); δ 0.88 (t, 3H).

4-dodecyloxyphenol (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol) and DMAP (p-dimethylaminopyridine) (1.7 g) synthesized in a flask , 13.9 mmol) was added, and 120 mL of methylene chloride was added, followed by reaction under nitrogen at room temperature for 24 hours. After completion of the reaction, the urea salt generated during the reaction was removed with a filter, and the remaining methylene chloride was also removed. In column chromatography, hexane and dichloromethane (DCM, dichloromethane) were used as mobile phases to remove impurities, and the obtained product was recrystallized in a mixed solvent of methanol and water (1:1 mixture) to obtain a white solid object (7.7 g, 22.2). mmol) in 63% yield.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): ?7.02 (dd, 2H); [delta] 6.89 (dd, 2H); δ 6.32 (dt, 1H); ?5.73 (dt, 1H); δ 3.94 (t, 2H); δ 2.05 (dd, 3H); delta 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 0.88 (t, 3H).

[Formula A]

In Formula A, R is a C12 linear alkyl group.

Preparation Example 2. Synthesis of Monomer (B)

In the following chemistry, the compound of B (ETFVB) was synthesized in the following manner. After adding pentafluorostyrene (15.0 g, 77.3 mmol) and ethanol (7.1 g, 154.6 mmol) to the flask, it was dissolved in tetrahydrofuran (THF, 250 mL) and cooled by immersing the flask in an ice bath. . Sodium hydroxide (4.0 g, 92.7 mmol) was added little by little to the reaction solution, and the flask was taken out to room temperature and reacted for about 8 hours (overnight). After the reaction was completed, extraction was performed with water and diethyl ether, and the organic layer was collected and columned with hexane to obtain a free liquid target (11.7 g, 53.1 mmol) in a yield of 69%.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 6.33 (dd, 1H); δ 6.03 (d, 1H); [delta]5.62(d, 1H); δ 4.29 (q, 2H); δ 1.42 (t, 3H).

[Formula B]

Compound of Preparation Example 1 (DPM-C12) 4.0 g and RAFT (Reversible Addition Fragmentation Chain Transfer) reagent (2-cyano-2-propyl-4-cyanobenzodithioate) 142.2 mg, AIBN (Azobisisobutyronitrile) 9.5 mg and anisole 9.69 mL was put into a 10 mL flask (Schlenk flask) and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 95° C. for 1 hour. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a pale pink macro initiator. The yield of the giant initiator was about 80% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 7,100 and 1.16, respectively.

0.45 g of the synthesized macroinitiator, 2.7908 g of the monomer of Formula B of Preparation Example 2, 0.0015 g of 1,1'-Azobis (cyclohexane-1-carbonitrile), and 3.2408 g of trifluorotoluene were added to a 10 mL flask (Schlenk flask) and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 95° C. for 3 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink block copolymer. The yield of the block copolymer was about 50%, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 18,100 and 1.18, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from the compound of Formula B of Preparation Example 2.

Example 2.

Compound of Preparation Example 1 (DPM-C12) 2.0 g and RAFT (Reversible Addition Fragmentation Chain Transfer) reagent (2-cyano-2-propyl benzodithioate) 28.3 mg, AIBN (Azobisisobutyronitrile) 10.5 mg and anisole (4.69 mL) After placing in a 10 mL flask (Schlenk flask) and stirring for 30 minutes at room temperature under a nitrogen atmosphere, RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 70° C. for 4 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a pale pink macro initiator. The yield of the giant initiator was about 78% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 14,200 and 1.19, respectively.

0.3 g of the synthesized macroinitiator, 1.8605 g of the monomer of Formula B in Preparation Example 2, 0.0017 g of Azobisisobutyronitrile (AIBN), and 2.171 mL of anisole were added to a 10 mL flask (Schlenk flask) and 30 minutes at room temperature under a nitrogen atmosphere. After stirring for 4 hours, RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 70°C. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink block copolymer. The yield of the block copolymer was about 45%, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 32,500 and 1.25, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from the compound of Formula B of Preparation Example 2.

Comparative Example 1

Compound of Preparation Example 1 (DPM-C12) 4.0 g and RAFT (Reversible Addition Fragmentation Chain Transfer) reagent (2-cyano-2-propyl-4-cyanobenzodithioate) 35.5 mg, AIBN (Azobisisobutyronitrile) 2.4 mg and anisole 9.4218 g was put into a 10 mL flask (Schlenk flask), stirred at room temperature under a nitrogen atmosphere for 30 minutes, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 95° C. for 1 hour. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a pale pink macro initiator. The yield of the giant initiator was about 72% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 15,500 and 1.18, respectively.

Put 0.45 g of the synthesized macroinitiator, 3.1181 g of pentafluorostyrene monomer, 0.0013 g of 1,1'-Azobis (cyclohexane-1-carbonitrile) and 3.9481 g of trifluorotoluene into a 10 mL flask (Schlenk flask). After stirring for 30 minutes at room temperature under a nitrogen atmosphere, RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization was performed at 95° C. for 20 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink block copolymer. The yield of the block copolymer was about 42%, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 33,100 and 1.28, respectively.

The GPC measurement results for each of the macroinitiators and the prepared block copolymers of the above examples are summarized and described in Table 1 below.

Example Comparative example One 2 MI Mn 7100 14200 15500 PDI 1.16 1.19 1.18 BCP Mn 18100 32500 33100 PDI 1.18 1.25 1.28

MI: Giant initiator

BCP: block copolymer

Test Example 1.

A self-assembled polymer film was formed using the block copolymer synthesized in Example 1, and the results were confirmed. Specifically, a coating solution prepared by dissolving the copolymer in a solvent at a concentration of about 1.0% by weight is spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and self-assembled block copolymer through thermal annealing A film containing was formed. Thereafter, a scanning electron microscope (SEM) photograph was taken on the polymer film to evaluate the self-assembly efficiency. 1 is a result of phase separation for Example 1, and it can be seen that the block copolymer forms a self-assembled structure that is evenly aligned on the substrate.

Test Example 2.

A self-assembled polymer film was formed using the block copolymer synthesized in Example 2, and the results were confirmed. Specifically, a coating solution prepared by dissolving the copolymer in a solvent at a concentration of about 1.0% by weight is spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds, and self-assembled block copolymer through thermal annealing A film containing was formed. Thereafter, a scanning electron microscope (SEM) photograph was taken on the polymer film to evaluate the self-assembly efficiency. FIG. 2 is a result of the phase separation for Example 2, and it can be seen that the block copolymer forms a self-assembled structure in which the block copolymer is evenly oriented vertically on the substrate, and the vertically oriented self-assembled structure is also formed under the polymer film.

Test Example 3

The experiment was conducted under the same conditions as in Test Example 2, except that a self-assembled polymer film was formed using the block copolymer synthesized in Comparative Example 1. 3 is a phase separation result for the comparative example, through which it can be seen that the block copolymer fails to form a self-assembled structure that is evenly aligned on the substrate, and that a defect occurs in the self-assembled structure of the polymer film. It can be seen that the lamellar structure and the horizontally oriented lamellar structure are mixed.

Claims (15)

A first block having a unit represented by Formula 1 below; And a second block having a unit represented by the following Chemical Formula 5,
The number average molecular weight (Mn) is in the range of 16,500 to 40,000,
The second block is a block copolymer containing only the unit of Formula 5:
[Formula 1]

[Formula 5]

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 alkenylene group, an alkynylene group,- 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 alkenylene group, or an alkynyl A ren group, and Y is a monovalent substituent including a ring structure connected to a straight chain having 8 or more chain forming atoms,
In Formula 5, X ₂ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -alkylene group, alkenylene group, alkynylene group, -C(=O)-X ₃ -or -X _3- C(=O)-, wherein X ₃ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and R ₁ to R ₅ are each independently represents a hydrogen, an alkyl group, a haloalkyl group, a halogen atom or an alkoxy group, R ₁ to R ₅ in R ₃ is an alkoxy group having 1 to 4 carbon atoms, the number of halogen atoms, including the R ₁ to R ₅ is at least one .
The block copolymer of claim 1, wherein X is a single bond, an oxygen atom, -C(=O)-O-, or -OC(=O)-.
The block copolymer of claim 1, wherein the linear chain includes 8 to 20 chain forming atoms.
The block copolymer according to claim 1, wherein the chain forming atoms are carbon, oxygen, nitrogen or sulfur.
The block copolymer of claim 1, wherein the straight chain is a hydrocarbon chain.
The block copolymer according to claim 1, wherein the ring structure of Y is an aromatic ring structure or an alicyclic ring structure.
The method of claim 1, wherein the straight chain of Y is connected to the ring structure through a linker, and the linker is an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an Al It is a kenylene group or an alkynylene group, wherein R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group.
The block copolymer of claim 1, wherein Y is represented by the following formula:
[Formula 2]

In Formula 2, P is an arylene group, Q is a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is 8 It is a straight chain having the above chain forming atoms.
The block copolymer according to claim 1, wherein the number of halogen atoms contained in R ₁ to R ₅ is 3 or more.
The block copolymer according to claim 1, wherein the halogen atom is a fluorine atom.
delete delete A polymer film comprising the self-assembled block copolymer of claim 1.
A method for forming a polymer film comprising forming a polymer film comprising the block copolymer of claim 1 self-assembled on a substrate.
A pattern comprising a process of selectively removing the first block or the second block of the block copolymer from a laminate having a substrate and a polymer film formed on the substrate and comprising a self-assembled block copolymer of claim 1 Formation method.

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