TW201538548A - Block copolymer - Google Patents

Abstract

The present application provides the block copolymers and their application. The block copolymer has an excellent self assembling property and phase separation and various required functions can be freely applied thereto as necessary.

Description

Block copolymer

This invention relates to block copolymers.

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

The present invention provides block copolymers and uses thereof.

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

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

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

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

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

The term "aryl" or aryl aryl as used herein may be self-contained in a benzene ring structure or in which at least two benzene rings are shared to share one or two A monovalent or divalent structure derived from a carbon atom or a compound having a structure linked by a random linker, or a derivative of a compound, unless otherwise defined. The aryl or extended aryl group may be an aryl group having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms unless otherwise defined.

The term "inden aromatic structure" as used herein may mean aryl or aryl.

The term "resin ring structure" as used herein may refer to a cyclic hydrocarbon structure that is not an aromatic cyclic structure. The lipid ring structure may be a structure having 3 to 30, 3 to 25, 3 to 21, 3 to 18, or 3 to 13 carbon atoms unless otherwise defined.

The term 〝 single bond 如 as used herein may refer to an example in which no atom is present at a corresponding position. For example, an example in which 〝B〞 is a single bond in a structure represented by 〝ABC〞 means that there is no atom at the 〝B〞 position, and thus the structure represented by 〝AC〞 is directly connected to 〝A〞 C〞 formed.

The substituent which may optionally be substituted for an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryl group, a chain, an aromatic structure or the like may be a hydroxyl group. , halogen atom, carboxyl group, glycidyl group, acryl fluorenyl group, methacryl fluorenyl group, acryloxy group, methacryloxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, stretching Alkenyl, alkynyl, alkoxy or aryl, but is not limited thereto.

In one embodiment, a monomer represented by Formula 1 below having a novel structure and capable of forming a block copolymer can be provided.

In Formula 1, R hydrogen or alkyl, and X is a single bond, 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)-. In the above formula, X ₁ may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an alkynyl group, and Y may be included and have 8 or more forming chains. A monovalent substituent of a cyclic structure linked by a chain of atoms.

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

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

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

When the compound of Formula 1 forms a block copolymer, the block copolymer can exhibit excellent self-assembly properties due to the presence of the chain.

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

In Formula 1, Y may include a ring structure. The chain can be attached to the ring structure. The self-assembling properties of the block copolymer formed from the compound can be further improved due to the cyclic structure. The cyclic structure may be an aromatic structure or a lipid ring structure.

The chain may be directly attached to the ring structure or may be attached to the ring structure via a linker. Oxygen atom, sulfur atom, -NR ₁ -, -S(=O) ₂ -, carbonyl, alkylene, alkenyl, alkynyl, -C(=O)-X ₁ - or -X ₁ -C (=O)- can be exemplified by a linking group. In the above formula, R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X1 may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O ₂ - an alkylene group, an alkenyl group or an alkynyl group, and in the above formula, R ₂ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group. A suitable linking group can be an oxygen atom or a nitrogen atom. For example, the chain can be attached to the aromatic structure via an oxygen or nitrogen atom. In this example, the linking group can be an oxygen atom or -NR ₁ -, wherein R ₁ can be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl.

In one embodiment, Y of Formula 1 can be represented by Formula 2.

[Formula 2] -PQZ

In Formula 2, P may be an extended aryl group, and Q may be a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z can be a chain of atoms having at least 8 chains forming a chain. In the example in which Y of Formula 1 is a substituent of Formula 2, P of Formula 2 may be directly bonded to X of Formula 1.

In Formula 2, a suitable P may be an extended aryl group having 6 to 12 carbon atoms, such as a phenyl group, but is not limited thereto.

In Formula 2, a suitable Q may be an oxygen atom or -NR ₁ -, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl.

Wherein R is a hydrogen atom or an alkyl group; or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, and Y is a substituent of the formula 2, wherein P is 6 A monomer of formula 1 up to a aryl group of 12 carbon atoms or a phenyl group, Q being an oxygen atom, and Z being a chain of 8 or more chain-forming atoms may be exemplified by the monomer of formula 1 The implementation of the situation.

Therefore, the monomer of the following formula 3 can be exemplified as a suitable embodiment.

In Formula 3, 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 oxygen. An atom, and Z is the above chain having 8 or more atoms forming a chain.

Another embodiment of the present invention is directed to a method for preparing a block copolymer comprising the step of forming a block by polymerizing a monomer.

The specific method for producing the block copolymer is not particularly limited as long as it comprises a step of forming at least one block of the block copolymer by using the above monomers.

For example, block copolymers can be prepared by living radical polymerization (LRP) using monomers. For example, there are methods such as anionic polymerization in which a block copolymer is an organic rare earth metal complex or an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as a salt of an alkali metal or an alkaline earth metal. Synthesis; anionic polymerization in which a block copolymer is synthesized using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound; atom transfer radical polymerization using an atom transfer radical polymerization agent as a polymerization control agent (ATRP); ATRP by electron transfer regeneration activator (ATGET) in the presence of an organic or inorganic reducing agent that produces electrons Polymerization using an atom transfer radical polymerization agent as a polymerization control agent; ATRP by a continuous activator regeneration initiator (ICAR); reversible addition using an inorganic reducing agent-reversible addition of a ring-opening chain transfer agent - Open-loop chain transfer (RAFT) polymerization; and a method using an organic ruthenium compound as an initiator, and an appropriate method can be selected among the above methods.

In one embodiment, the block copolymer can be prepared by a method comprising living a free radical polymerization of a material comprising a monomer capable of forming a block in the presence of a free radical initiator and a living radical polymerization reagent. polymerization.

In the preparation of the block copolymer, the method for forming the other block included in the block copolymer together with the block formed of the above monomer is not particularly limited, and other monomers can be considered It is formed by selecting an appropriate monomer to the type of the block to be formed.

The method for preparing the block copolymer may additionally include precipitating the polymerization product produced by the above method in a non-solvent.

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

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

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

Still another embodiment of the present invention is directed to a block copolymer comprising a block formed using a monomer (hereinafter may be referred to as a first block).

The block can be represented, for example, by Formula 4.

In Formula 4, R, X and Y may be the same as those described for R, X and Y of Formula 1, respectively.

Therefore, in Formula 4, R may be hydrogen or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, An alkenyl group, an alkynyl group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, An alkyl group, an alkenyl group or an alkynyl group, and Y may be a monovalent substituent including a cyclic structure linked to a chain having 8 or more chains forming an atom. The above description can be applied in the same manner to the specific type of each of the above substituents.

In one embodiment, the first block can be a block of formula 4 wherein R is hydrogen or an alkyl group; or hydrogen or an alkane having from 1 to 4 carbon atoms A group, X is -C(=O)-O-, and Y is a substituent represented by Formula 2. Such a block may be referred to as a 1A block, but is not limited thereto. This block can be represented by the following formula 5.

In Formula 5, R may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, -C(=O)-O- or -OC(=O)-, P. It may be an aryl group, Q may be an oxygen atom or -NR ₃ -, wherein R ₃ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and Z has 8 or more chains The chain of atoms. In another embodiment, Q of Formula 5 can be an oxygen atom.

In another embodiment, the first block can be a block represented by Formula 6. Such a first block may be referred to herein as a 1B block.

In Formula 6, R ₁ and R ₂ may each independently be hydrogen or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, An alkyl 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, or a -S (=O) ₂ -, alkyl, alkenyl or alkynyl, T may be a single bond or an aryl group, Q may be a single bond or a carbonyl group, and Y may be an atom having at least 8 chains forming a chain chain.

In the block of 1B of Formula 6, X may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -O-C(=O)-.

The above description regarding Formula 1 can be applied in the same manner as a special embodiment of the chain Y in the 1B block.

In another embodiment, the first block may be a block represented by at least one of Formulas 4 to 6, wherein at least one of the chains having 8 or more chain-forming atoms forms a chain of atoms The electronegativity is 3 or more. In another embodiment, the electrons forming the atoms of the chain may have an electronegativity of 3.7 or less. Such a block may be referred to herein as a 1C block. A nitrogen atom or an oxygen atom may be exemplified as an atom having an electronegativity of 3 or more, but is not limited thereto.

The kind of another block included in the block copolymer together with the first block such as the 1A, 1B or 1C block (hereinafter may be referred to as a second block) is not particularly limited.

For example, the second block can be a polyvinylpyrrolidone block, a polylactic acid block, a polyvinylpyridine block, a polystyrene block (such as a polystyrene block or a polytrimethyldecyl styrene). a polyalkylene oxide block (such as a polyethylene oxide block) or a polyolefin block (such as a polyethylene block or a polyisoprene block or a polybutadiene block). Such a block as used herein may be referred to as a 2A block.

In one embodiment, the second block included in the block copolymer together with the first block (such as the 1A, 1B or 1C block) may be a block comprising an aromatic structure comprising At least one halogen atom.

Such a second block may be represented, for example, by the following formula 7 and may be referred to as a 2B block.

In Formula 7, B may be a monovalent substituent having an aromatic structure including at least one halogen atom.

Such a second block can effectively interact with the first block described above such that the block copolymer can have excellent self-assembly characteristics.

The aromatic structure of Formula 7 can be, for example, from 6 to 18 or 6 to An aromatic structure of 12 carbon atoms.

Further, the halogen atom included in the formula 7 may be, but not limited to, a fluorine atom or a chlorine atom, and is preferably a fluorine atom.

In one embodiment, B of Formula 7 may be a monovalent substituent having an aromatic structure of 6 to 12 carbon atoms, the aromatic structure being 1 or more, 2 or more, 3 or more, 4 Or more, or substituted with 5 or more halogen atoms. The upper limit of the number of halogen atoms is not particularly limited, but it may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

For example, the block represented by Formula 7 (which is a 2B block) can be represented by the following Formula 8.

In Formula 8, 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 An aryl group substituted with at least one halogen atom. In the above formula, W may be an aryl group substituted with at least one halogen atom, for example, having 6 to 12 carbon atoms and having 2 or more, 3 or more, 4 or more, or 5 or more halogens An atom-substituted aryl group.

The 2B block can be represented, for example, by the following formula 9.

In Formula 9, 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 alkenyl group or an alkynyl group, 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 9, in another embodiment, X ₂ may be a single bond, an oxygen atom, an alkylene group, -C(=O)-O- or -OC(=O)-.

In Formula 9, R ₁ to R ₅ may each independently be a hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and R ₁ to R ₅ may include 1 or more, 2 or more, 3 or more, 4 Or more, or 5 or more halogen atoms, such as a fluorine atom. The number of halogen atoms (such as fluorine atoms) included in R ₁ to R ₅ may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less.

In one embodiment, the second block can be a block represented by Formula 10. Such a block as used herein may be referred to as a 2C block.

In Formula 10, T and K may each independently be an oxygen atom or a single bond, and U may be an alkylene group.

In one embodiment, in the 2C block, U of Formula 10 can be an alkylene group having from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 8, or from 1 to 4 carbon atoms.

In another embodiment, the 2C block can be a block of formula 10, wherein one of T and K of formula 10 is a single bond, and the other of T and K of formula 10 is an oxygen atom. In the above block, U may be an alkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms.

In yet another embodiment, the 2C block can be a block of formula 10 wherein both T and K of formula 10 are oxygen atoms. In the above block, U may be an alkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms.

In yet another embodiment, the second block can be a block comprising at least one metal atom or metalloid. Such a block can be referred to as a 2D block. This block can improve the etch selectivity when an etching method is performed with respect to, for example, a film including a self-assembled block copolymer.

The metal atom or metalloid atom in the 2D block may be a germanium atom, an iron atom or a boron atom, but is not particularly limited as long as it exhibits a suitable etching due to being different from another atom in the block copolymer. Selectivity.

The 2D block may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms together with a metal or metalloid atom, such as a fluorine atom. The 2D block may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms such as a fluorine atom.

The 2D block can be represented by Formula 11.

In Formula 11, B may be a monovalent substituent having an aromatic structure including a halogen atom and a substituent having a metal atom or a metalloid atom.

The aromatic structure of Formula 11 may be an aromatic structure having 6 to 12 carbon atoms, such as an aryl group or an aryl group.

The 2D block of Formula 11 can be represented by Formula 12 below.

In Formula 12, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O) -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ is a single bond, an oxygen atom, a sulfur atom , -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, and W may be an aryl group including at least one halogen atom and a substituent including a metal atom or a metalloid atom .

In the above formula, W may be an aryl group having 6 to 12 carbon atoms and including at least one halogen atom and a substituent including a metal atom or a metalloid atom.

The aryl group may include at least 1 or 1 to 3 substituents including a metal atom or a metalloid atom and 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogens atom.

These may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

The 2D block of Formula 12 can be represented by Formula 13 below.

In Formula 13, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O) -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and each of R ₁ to R ₅ may independently be hydrogen, an alkyl group, a haloalkyl group, a halogen atom or A substituent including a metal or metalloid atom is presupposed that at least one of R ₁ to R ₅ includes a halogen atom, and at least one of R ₁ to R ₅ is a substituent including a metal or a metalloid atom.

In Formula 13, one or more of R ₁ to R ₅ , 1 to 3 or 1 to 2 may be a substituent including a metal or a metalloid atom.

In Formula 13, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms may be included in R ₁ to R ₅ . The number of halogen atoms included in R ₁ to R ₅ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The above substituent including a metal or metalloid atom may be carbon A carboranyl group or a sesquiterpoxyalkyl group (such as a polyhedral oligomeric sesquiterpoxyalkyl group), a ferrocenyl group or a trialkyldecyloxy group. However, these are not particularly limited as long as the selected ones include at least one metal or metalloid atom in order to obtain etching selectivity.

In still another embodiment, the second block may be a block including an atom which is an atom having an electronegativity of 3 or more and which is a non-halogen atom (hereinafter referred to as a non-halogen atom) ). Such a block can be referred to as a 2E block. In another embodiment, the non-halogen atom in the 2E block may have an electronegativity of 3.7 or less.

The non-halogen atom in the 2E block may be, but not limited to, a nitrogen atom or an oxygen atom.

The 2E block may include a non-halogen atom having an electronegativity of 3 or more and 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms, such as fluorine. atom. The number of halogen atoms (such as fluorine atoms) in the 2E block may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The 2E block can be represented by Formula 14.

In Formula 14, B may be a monovalent substituent having an aromatic structure including a substituent having a non-halogen atom having an electronegativity of 3 or more and including a halogen atom.

The aromatic structure of Formula 14 may be an aromatic structure having 6 to 12 carbon atoms, such as an aryl group or an aryl group.

In another embodiment, the block of Formula 14 can be represented by Formula 15.

In Formula 15, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O) -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and W may be an aryl group including a substituent and at least one halogen atom, the substituent including A non-halogen atom of 3 or greater electronegativity.

In the above formula, W may be an aryl group having 6 to 12 carbon atoms, including a substituent and including at least one halogen atom, and the substituent includes a non-halogen atom having an electronegativity of 3 or more.

Such an aryl group may include at least 1 or 1 to 3 substituents including a non-halogen atom having an electronegativity of 3 or more. Further, the aryl group may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. In the above formula, the aryl group may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

In another embodiment, the block of Formula 15 can be represented by Formula 16.

In Formula 16, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, a -C(=O) group. -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and each of R ₁ to R ₅ may independently be a hydrogen, an alkyl group, a haloalkyl group or a halogen atom. And a substituent including a non-halogen atom having an electronegativity of 3 or more. In the above formulas, R ₁ to R ₅ is at least one of a halogen atom, and R ₁ to R ₅ is at least one of which is 3 include a halogen atom, or a non-negative power of the larger substituents.

In Formula 16, at least one of R ₁ to R ₅ , 1 to 3, or 1 to 2 may be the above-mentioned substituent including a non-halogen atom having an electronegativity of 3 or more.

In Formula 16, R ₁ to R ₅ may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. R ₁ to R ₅ may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

The above substituent including a non-halogen atom having an electronegativity of 3 or more may be, but not limited to, a hydroxyl group, an alkoxy group, a carboxyl group, a decylamino group, an oxiranyl group, a nitrile group, a pyridyl group or an amine group.

In another embodiment, the second block can include an aromatic structure having a heterocyclic substituent. Such a second block may be referred to herein as a 2F block.

The 2F block can be represented by Formula 17.

In Formula 17, B may be a monovalent substituent having an aromatic structure having 6 to 12 carbon atoms and substituted with a heterocyclic substituent.

The aromatic structure of Formula 17 may include at least one halogen atom, if necessary.

The block of Formula 17 can be represented by Formula 18.

In Formula 18, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, a -C(=O) group. -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, A sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and W may be an aryl group having 6 to 12 carbon atoms and having a heterocyclic substituent.

The block of Formula 18 can be represented by Formula 19.

In Formula 19, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O) -X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and each of R ₁ to R ₅ may independently be a hydrogen, an alkyl group, a haloalkyl group or a halogen atom. Or a heterocyclic substituent. In the above formula, at least one of R ₁ to R ₅ is a heterocyclic substituent.

In Formula 19, at least one of R ₁ to R ₅ (for example, 1 to 3 or 1 to 2) may be a heterocyclic substituent, and the other may be a hydrogen atom, an alkyl group or a halogen atom; or hydrogen An atom or a halogen atom; or a hydrogen atom.

The above heterocyclic substituent may be, but not limited to, a substituent derived from a quinone imine, a substituent derived from thiopene, a substituent derived from a thiazole, a substituent derived from a carbazole or a self-derived group. Substituents derived from imidazole.

The block copolymer of the present invention may include at least one of the above first blocks and at least one of the above second blocks. Such block copolymers may include 2 or 3 blocks, or 3 or more blocks. In one embodiment, the block copolymer can be a diblock copolymer comprising any of the first block and the second block.

Such block copolymers can exhibit substantially excellent self-assembly properties or phase separation properties. Further, if the block is selected and combined in order to satisfy the block copolymer with at least one of the following parameters, the self-assembly property or the phase separation property can be further improved.

The block copolymer can be phase separated because it comprises two or more polymer chains joined to each other via a covalent bond. The block copolymer of the present invention exhibits excellent phase separation properties, and if necessary, can be microphase-separated to form a nano-scale structure. The shape or size of the nanostructure can be determined by the size of the block copolymer (Molecular weight and similar) or the relative ratio of blocks is controlled. The structures formed by phase separation may include spheres, cylinders, gyroids, sheets, and inverted structures, and the ability to form the above structures may be referred to as self-assembly properties. Among the various block copolymers having various structures described above, the inventors have confirmed that a block copolymer satisfying at least one of the following parameters can exhibit substantially self-assembled properties of the block copolymer which is further improved. The block copolymer may satisfy one of the following parameters or two or more of the following parameters. In particular, it has been confirmed that it is possible to exhibit a vertical alignment property of a block copolymer by satisfying a block copolymer of an appropriate parameter. The term "vertical alignment property" as used herein may refer to the alignment properties of a block copolymer and may refer to an example in which the nanostructure formed by the block copolymer is oriented perpendicular to the substrate. Techniques for controlling the vertical or parallel alignment of self-assembled structures of block copolymers with respect to various substrates are a significant part of the practical application of block copolymers. The alignment of the nanoscale structure in the block copolymer layer is conventionally dependent on which of the blocks forming the block copolymer is exposed to the surface or air. In general, because many substrates are polar and air is non-polar, blocks having a higher polarity than other blocks in the block copolymer are wet on the substrate and have more blocks than other blocks in the block copolymer. The low polarity block wets the interface between the air. Accordingly, many techniques have been proposed for simultaneously wetting substrates with blocks having different properties of the block copolymers, and the most typical method is to control alignment by preparing a neutral surface. However, in one embodiment, the block copolymer can be vertically aligned relative to the substrate by controlling the following parameters without conventionally known processing to achieve vertical alignment, including neutral surface treatment. Furthermore, in addition In the embodiment, the vertical alignment with respect to a large area can be achieved in a short time by thermal annealing.

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

As used herein, the term "grain angle incident small angle X-ray scattering (GISAXS) shows in-plane phase diffraction pattern 〞 may refer to a peak perpendicular to the X coordinate observed on the GISAXS diffraction pattern when performing GISAXS analysis. example. Such peaks can be determined by the vertical alignment properties of the block copolymer. Therefore, the block copolymer showing the in-plane phase diffraction pattern exhibits a vertical alignment property. In another embodiment, two or more peaks can be observed on the X coordinate of the GISAXS diffraction pattern. In the example in which two or more peaks are observed, the scattering vector (q value) can be confirmed with a constant ratio, and the phase separation efficiency can be further improved in the above examples.

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

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

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

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

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

When performing X-ray diffraction (XRD) analysis, the block copolymer can exhibit at least one peak within a particular scattering vector (q value).

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

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

The term 〝FWHM (full width at half maximum) as used herein may refer to a peak at a position where the display intensity is half of the maximum intensity. Width (the difference between the scattering vectors (q)).

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

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

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

As described below, in the example in which at least one block of the block copolymer includes a chain, the number of atoms forming the chain (n) and the scattering vector (q) obtained from the XRD analysis can satisfy the following Equation 1.

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

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

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

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

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

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

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

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

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

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

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

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

The block copolymer may have a number average molecular weight (Mn) ranging, for example, from about 3,000 to 300,000. The term 〝 number average molecular weight 〞 as used herein may refer to a conversion value relative to standard polystyrene measured by GPC (gel permeation chromatography). The term "molecular weight" as used herein may refer to a number average molecular weight unless otherwise defined. In another embodiment, the molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7,000 or more, 9000 or more, 11,000 or more, 13,000 or more, or 15,000 or more. . In another embodiment, the molecular weight (Mn) may be, for example, 250,000 or less, 200,000 or less, 180,000 or less, 160,000 or less, 140,000 or less, 120,000 or less, 100,000 or less, 90000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, or 25,000 or less. The block copolymer may have a polydispersity (Mw/Mn) in the range of from 1.01 to 1.60. In another embodiment, the polydispersity can be about 1.1 or Larger, about 1.2 or greater, about 1.3 or greater, or about 1.4 or greater.

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

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

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

In one embodiment, the block copolymer in the polymer layer can form a periodic structure by self-assembly, including spheres, cylinders, pentagonal tetrahedrons or sheets.

For example, in the first block or the second block in the block copolymer or in one segment of the other block of the above block via a covalent bond, the other segments may form a regular structure, such as a sheet Form, cylinder form and the like.

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

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

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

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

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

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

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

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

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

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

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

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

Figures 1 through 15 are SEM or AFM images of the polymer layer and show the results of the GISAXS analysis of the polymer layer.

Figures 16 to 20 show the results of the GISAXS of the polymer layer.

effect

The present invention can provide block copolymers and applications thereof. The block copolymer has excellent self-assembly properties and phase separation, and can be freely subjected to various necessary functions as necessary.

Exemplary implementation

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

NMR analysis

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

<abbreviation>

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

2. GPC (gel permeation chromatography)

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

<GPC measurement conditions>

Device: 1200 Series from Agilent technologies, Co.

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

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / ml, 200 L injection

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

Preparation Example 1

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

<NMR analysis results of intermediates>

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

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

<About NMR analysis results of DPM-C12>

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

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

Preparation Example 2

The compound of the following formula B (DPM-C8) was synthesized according to the method of Preparation 1, except that 1-bromooctane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C8>

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

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

Preparation Example 3

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

<About NMR analysis results of DPM-C10>

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

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

Preparation Example 4

The compound of the following formula D (DPM-C14) was synthesized according to the method of Preparation 1, except that 1-bromotetradecane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C14>

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

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

Preparation Example 5

The compound of the following formula E (DPM-C16) was synthesized according to the method of Preparation 1, except that 1-bromohexadecane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<About NMR analysis results of DPM-C16>

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

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

Preparation Example 6

The compound of the following formula F (DPM-N2) was synthesized by the following method. Pd/C (palladium on carbon) (1.13 g, 1.06 mmol) and 200 ml 2-propanol were added to a 500 ml flask, followed by the addition of ammonium formate dissolved in 20 ml of water, and then at room temperature A 1 minute reaction was carried out to activate Pd/C. Next, 4-aminophenol (1.15 g, 10.6 mmol) and lauric anhydride (1.95 g, 10.6 mmol) were added thereto, and the mixture was mixed by stirring at room temperature under nitrogen for 1 minute. After the reaction, Pd/C was removed and 2-propanol for the reaction was removed, and then the mixture was extracted with water and dichloromethane to remove unreacted product. The organic layer was collected and dehydrated by MgSO _4. The crude product was purified by column chromatography (mobile phase: hexane/ethyl acetate), to give a colorless solid intermediate (1.98 g, 7.1 mmol) (yield: 67%).

<Results of NMR analysis of intermediates>

¹ H-NMR (DMSO-d): δ 6.69 (dd, 2H); δ 6.53 (dd, 2H); δ 3.05 (t, 2H); δ 1.59 (p, 2H); δ 1.40- 1.26(m,16H);δ0.88(t,3H)

The intermediate was synthesized (1.98 g, 7.1 mmol), methacrylic acid (0.92 g, 10.7 mmol), dicyclohexylcarbodiimide (DCC; 2.21 g, 10.7 mmol) and Dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmol) was placed in a flask, 100 ml of dichloromethane was added, and the reaction was carried out under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt produced during the reaction was removed via a filter and the remaining dichloromethane was also removed. The impurities were removed via column chromatography using hexane and DCM (dichloromethane) as the mobile phase, and the obtained product was in a mixed solvent of methanol and water (methanol: water = 3:1 (weight ratio)) Crystallization, whereby a white solid product (DPM-N2) (1.94 g, 5.6 mmol) having a yield of 79% was obtained.

<Results of NMR analysis on DPM-N2>

¹ H-NMR (CDCl ₃ ): δ 6.92 (dd, 2H); δ 6.58 (dd, 2H); δ 6.31 (dt, 1H); δ 5.70 (dt, 1H); δ 3.60 (s) ,1H);δ3.08(t,2H);δ2.05(dd,3H);δ1.61(p,2H);δ1.30-1.27(m,16H);δ0.88(t,3H)

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

Preparation Example 7

The compound of the following formula G (DPM-C4) is according to Preparation Example 1. The method was synthesized except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results regarding the above compounds are as follows.

<Results of NMR analysis on DMP-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)

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

Example 1

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

0.3 g of the giant initiator, 2.7174 g of pentafluorostyrene and 1.306 ml of benzene were added to a 10 ml Schlenk flask and then stirred at room temperature for 30 minutes, and then subjected to RAFT at 115 ° C for 4 hours (reversible addition) Fracture chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, vacuum filtered and dried to obtain a light pink block copolymer. The yield of the block copolymer was about 18%, and the number average molecular weight (Mn) and polydispersity (Mw/Mn) thereof were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from pentafluorostyrene.

Example 2

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator and pentafluorobenzene prepared by using the compound of Preparation Example 2 (DPM-C8) instead of the compound of Preparation Example 1 (DPM-C12) were used. Other than ethylene. The block copolymer includes a first block derived from the compound of Preparation Example 2 (DPM-C8) and a second block derived from pentafluorostyrene.

Example 3

The block copolymer was prepared in the same manner as in Example 1, Except that the macroinitiator prepared by using the compound of Preparation Example 3 (DPM-C10) in place of the compound of Preparation Example 1 (DPM-C12) and pentafluorostyrene were used. The block copolymer includes a first block derived from the compound of Preparation Example 3 (DPM-C10) and a second block derived from pentafluorostyrene.

Example 4

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator and pentafluorobenzene prepared by using the compound of Preparation Example 4 (DPM-C14) in place of the compound of Preparation Example 1 (DPM-C12) and pentafluorobenzene were used. Other than ethylene. The block copolymer includes a first block derived from the compound of Preparation Example 4 (DPM-C14) and a second block derived from pentafluorostyrene.

Example 5

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator and pentafluorobenzene prepared by using the compound of Preparation Example 5 (DPM-C16) instead of the compound of Preparation Example 1 (DPM-C12) were used. Other than ethylene. The block copolymer includes a first block derived from the compound of Preparation Example 5 (DPM-C16) and a second block derived from pentafluorostyrene.

Example 6 Monomer synthesis

3-Hydroxy-1,2,4,5-tetrafluorostyrene was synthesized according to the following method. Pentafluorostyrene (25 g, 129 mmol) was added to a mixed solution of 400 ml of tertiary butanol and potassium hydroxide (37.5 g, 161 mmol); and then subjected to a reflux reaction for 2 hours. After the reaction, the product was cooled to room temperature, 1200 ml was added and the remaining butanol used for the reaction was volatilized. The adduct was extracted 3 times with diethyl ether (300 ml), and the aqueous layer was acidified with a 10% by weight hydrochloric acid solution until its pH became 3, and the title product was precipitated therefrom. The precipitated product was extracted 3 times with diethyl ether (300 mL) and organic layer was collected. The organic layer was anhydrified on MgSO ₄ and the solvent removed. The crude product was purified by column chromatography using hexanes and DCM (dichloromethane) as mobile phase, and thus obtained as a colorless liquid 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g) ). The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (DMSO-d): δ 11.7 (s, 1H); δ 6.60 (dd, 1H); δ 5.89 (d, 1H); δ 5.62 (d, 1H)

Synthesis of block copolymer

AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyldodecyl trisulfate) and the compound of Preparation Example 1 (DPM-C12) ) dissolved in benzene in a weight ratio of 50:1:0.2 (DPM-C12: RAFT reagent: AIBN) Degree: 70% by weight), and then a giant initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2) was prepared by reacting the mixture at 70 ° C for 4 hours under nitrogen. Then the synthetic macroinitiator, 3-hydroxy-1,2,4,5-tetrafluorostyrene (TFS-OH) and AIBN (azobisisobutyronitrile) in a weight ratio of 1:200:0.5 (giant The initiator: TFS-OH: AIBN) was dissolved in benzene (concentration: 30% by weight), and then a block copolymer was prepared by reacting the mixture at 70 ° C for 6 hours under nitrogen to obtain a number average molecular weight: 35,000. Polydispersity: 1.2). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block derived from 3-hydroxy-1,2,4,5-tetrafluorostyrene.

Example 7 Monomer synthesis

The compound of the following formula H was synthesized according to the following method.酞醯imine (10.0 g, 54 mmol) and chloromethylstyrene (8.2 g, 54 mmol) were added to 50 ml of DMF (dimethylformamide) and then at 55 ° C The reaction was carried out under nitrogen for 18 hours. After the reaction, 100 ml of ethyl acetate and 100 ml of distilled water were added to the reaction product, and then the organic layer was collected and then washed with a saline solution. The collected organic layer was treated with MgSO ₄ , and then water was removed, and then solvent was finally removed, and then recrystallized from pentane to give a white solid title compound (11.1 g). The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 7.84 (dd, 2H); δ 7.70 (dd, 2H); δ 7.40-7.34 (m, 4H); δ 6.67 (dd, 1H); δ 5.71 (d, 1H); δ 5.22 (d, 1H); δ 4.83 (s, 2H)

Synthesis of block copolymer

AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyldodecyl trisulfate) and the compound of Preparation Example 1 (DPM-C12) It was dissolved in benzene (concentration: 70% by weight) in a weight ratio of 50:1:0.2 (DPM-C12: RAFT reagent: AIBN), and then prepared by reacting the mixture at 70 ° C for 4 hours under nitrogen. Giant initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). The synthetic macroinitiator, the compound of formula H (TFS-PhIM) and AIBN (azobisisobutyronitrile) are then dissolved in a weight ratio of 1:200:0.5 (macroinitiator: TFS-PhIM: AIBN) In benzene (concentration: 30% by weight), and then the mixture was at 70. The mixture was reacted under nitrogen at ° C for 6 hours to prepare a block copolymer (number average molecular weight: 35,000, polydispersity: 1.2). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block derived from the compound of the formula H.

Example 8

0.8662 g of the compound of Preparation Example 1 (DPM-C12), 0.5 g of a macroinitiator (Macro-PEO) (poly(ethylene glycol)-4-cyano-4-(phenylothioyl)thio group) Valerate, weight average molecular weight (Mw): 10,000, Sigma Aldrich) (the two end sites are linked to RAFT (reversible addition-fragmentation chain transfer) reagent), 4.1 mg AIBN (azobisisobutyronitrile) and 3.9 Milligram of anisole was added to a 10 ml flask (Schlenk flask) and then stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT for 12 hours in a 70 ° C polyoxo oil container (reversible addition) - cleavage chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, followed by vacuum filtration and dried to obtain a light pink block copolymer (yield: 30.5%, number average molecular weight (Mn): 34,300, Polydispersity (Mw/Mn): 1.60). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of polyethylene oxide.

Example 9

2.0 g of the compound of Preparation Example 1 (DPM-C12), 25.5 mg of RAFT (reversible addition-fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 9.4 mg of AIBN (azobisisobutyronitrile) And 5.34 ml of benzene was added to a 10 ml flask (Schlenk flask) and stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT for 4 hours in a 70 ° C polyoxo oil container (reversible addition - Fracture chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, followed by vacuum filtration and drying to obtain a pink giant priming of the two end sites linked to the RAFT (reversible addition-fragmentation chain transfer) reagent. Agent. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the macroinitiator were 81.6 wt%, 15400 and 1.16, respectively. 1.177 g of styrene, 0.3 g of macroinitiator and 0.449 ml of benzene were added to a 10 ml flask (Schlenk flask) and stirred at room temperature for 30 minutes under nitrogen, and then in a 115 ° C polyoxo oil container. 4 hours of RAFT (reversible addition-fragmentation chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, followed by vacuum filtration and drying to prepare a pale pink novel block copolymer. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the block copolymer were 39.3% by weight, 31,800 and 1.25, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of polystyrene.

Example 10

0.33 g of the giant initiator prepared in Example 9, 1.889 g of 4-trimethyldecyl styrene, 2.3 mg of AIBN (azobisisobutyronitrile) and 6.484 ml of benzene were added to a 10 ml flask (Schlenk flask) and then stirred at room temperature for 30 minutes under nitrogen. Then, a RAFT (reversible addition-fragmentation chain transfer) polymerization reaction was carried out for 24 hours in a polyoxygenated oil container at 70 °C. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, followed by vacuum filtration and drying to prepare a pale pink novel block copolymer. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the block copolymer were 44.2% by weight, 29600 and 1.35, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of poly(4-trimethyldecylstyrene).

Example 11 Monomer synthesis

The compound of the following formula I was synthesized according to the following method. Pentafluorostyrene (25 g, 129 mmol) was added to a mixed solution of 400 ml of tertiary butanol and potassium hydroxide (37.5 g, 161 mmol); and then subjected to a reflux reaction for 2 hours. After the reaction, the product was cooled to room temperature, 1200 ml of water was added and the remaining butanol used for the reaction was volatilized. The adduct was extracted 3 times with diethyl ether (300 ml), and the aqueous layer was acidified with a 10% by weight hydrochloric acid solution until its pH became 3, and the title product was precipitated therefrom. The precipitated product was extracted 3 times with diethyl ether (300 mL) and organic layer was collected. The organic layer was anhydrified on MgSO ₄ and the solvent removed. The crude product was purified by column chromatography using hexanes and DCM (dichloromethane) as mobile phase, and thus a colorless liquid intermediate (3-hydroxy-1,2,4,5-tetrafluorostyrene) was obtained. ) (11.4 grams). The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (DMSO-d): δ 11.7 (s, 1H); δ 6.60 (dd, 1H); δ 5.89 (d, 1H); δ 5.62 (d, 1H)

The intermediate (11.4 g, 59 mmol) was dissolved in DCM (dichloromethane) (250 mL) and then imidazole (8.0 g, 118 mM), DMPA (p-dimethylaminopyridine) (0.29 g, 2.4 mmol) and tertiary butyl chlorodimethyl decane (17.8 g, 118 mmol) were added thereto. The mixture was stirred at room temperature for 24 hours and the reaction was quenched by the addition of 100 mL of brine, and then further extracted with DCM. The collected DCM organic layer was dried over MgSO ₄ and solvent was evaporated to afford crude product. After purification by column chromatography using hexanes and DCM as mobile phase, the product (10.5 g) was obtained as a colorless liquid. The NMR results of the underlying products are as follows.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 6.62 (dd, 1H); δ 6.01 (d, 1H); δ 5.59 (d, 1H); δ 1.02 (t, 9H), δ 0.23 (t , 6H)

Synthesis of block copolymer

AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyldodecyl trisulfate) and the compound of Preparation Example 1 (DPM-C12) It was dissolved in benzene (concentration: 70% by weight) in a weight ratio of 50:1:0.2 (DPM-C12: RAFT reagent: AIBN), and then prepared by reacting the mixture at 70 ° C for 4 hours under nitrogen. Giant initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). The synthetic macroinitiator, the compound of formula I (TFS-S) and AIBN (azobisisobutyronitrile) are then dissolved in benzene in a weight ratio of 1:200:0.5 (macroinitiator: TFS-S: AIBN). (Concentration: 30% by weight), and then a block copolymer (quantitative average molecular weight: 35,000, polydispersity: 1.2) was prepared by reacting the mixture at 70 ° C for 6 hours under nitrogen. The block copolymer includes the preparation example 1 The first block from which the compound is derived and the second block derived from the compound of formula I.

Example 12

AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) reagent (2-cyano-2-propyldodecyl trisulfate) and the compound of Preparation 6 (DPM-N1) ) was dissolved in benzene (concentration: 70% by weight) in a weight ratio of 26:1:0.5 (DPM-C12: RAFT reagent: AIBN), and then prepared by reacting the mixture at 70 ° C under nitrogen for 4 hours. Giant initiator (number average molecular weight: 9700, polydispersity: 1.2). The synthetic macroinitiator, pentafluorostyrene (PFS) and AIBN (azobisisobutyronitrile) are then dissolved in benzene in a weight ratio of 1:600:0.5 (macroinitiator: PFS: AIBN) (concentration: 30% by weight), and then a block copolymer (quantitative average molecular weight: 17300, polydispersity: 1.2) was prepared by reacting the mixture at 115 ° C for 6 hours under nitrogen. The block copolymer includes a first block derived from the compound of Preparation Example 6 and a second block derived from pentafluorostyrene.

Example 13

The block copolymer was prepared in the same manner as in Example 1 except that the macroinitiator and pentafluorobenzene prepared by using the compound of Preparation Example 7 (DPM-C4) instead of the compound of Preparation Example 1 (DPM-C12) were used. Other than ethylene. The block copolymer includes a first block derived from the compound of Preparation Example 7 (DPM-C4) and a second block derived from pentafluorostyrene. segment.

Comparative example 1

The block copolymer was prepared in the same manner as in Example 1, except that a giant initiator and pentafluorobenzene prepared by using 4-methoxyphenyl methacrylate instead of the compound of Preparation Example 1 (DPM-C12) were used. Other than ethylene. The block copolymer comprises a first block derived from 4-methoxyphenyl methacrylate and a second block derived from pentafluorostyrene.

Comparative example 2

The block copolymer was prepared in the same manner as in Example 1 except that a macroinitiator prepared by using the dodecyl methacrylate instead of the compound of Preparation Example 1 (DPM-C12) and pentafluorostyrene were used. The block copolymer comprises a first block derived from dodecyl methacrylate and a second block derived from pentafluorostyrene.

Test example 1

Self-assembled polymer layers were prepared by using the block copolymers of Examples 1 to 13 and Comparative Examples 1 and 2 and observed. Specifically, each block copolymer was dissolved in a solvent to a concentration of 1.0% by weight and then spin-coated on a tantalum wafer at a speed of 3000 rpm for 60 seconds. Self-assembly is then carried out by solvent annealing or thermal annealing. The solvents and aging methods used are set forth in Table 1 below. The polymer layers are then subjected to SEM (scanning electron microscopy) or AFM (atomic force microscopy) analysis to evaluate self-assembly. nature. 1 to 13 are the results of Examples 1 to 13, respectively, and Figs. 14 and 15 are the results of Comparative Examples 1 and 2, respectively.

Test example 2

From Test Example 1, it was confirmed that the block copolymer in the examples had substantially excellent self-assembly properties. In the examples, the assessment is about The GISAXS (grazing angle incident small angle X-ray scattering) property of the block copolymer prepared in Example 1. The above properties were evaluated in the 3C beam path of the Pohang Light Source. The polymer layer is formed by spin-coating a coating solution prepared by dissolving the block copolymer of Example 1 in fluorobenzene so as to have a solid content of 0.7% by weight, having hydrophilicity or hydrophobicity. On the substrate of the surface so that the coating has a layer of 5 nm thickness (coating area: width = 1.5 cm, length = 1.5 cm), and the layer is dried at room temperature for about 1 hour, and then This layer was subjected to thermal annealing at about 160 ° C for about 1 hour. The formed polymer layer is irradiated with X-rays so that the incident angle is from about 0.12 degrees to 0.23 degrees, which corresponds to the angle between the critical angle of the layer and the critical angle of the substrate, and is then obtained by using a 2D marCCD. The layer scatters the X-ray diffraction pattern. At this point, the distance from the layer to the detector is selected to effectively observe the self-assembled pattern in the layer from about 2 meters to 3 meters. A substrate having a wetting angle of about 5 degrees with respect to purified water at room temperature was used as a substrate having a hydrophilic surface, and a substrate having a wetting angle of about 60 degrees with respect to purified water at room temperature was used as a substrate having a hydrophobic surface. . Figure 16 is a graph showing the results of a GISAXS (grazing angle incident small angle X-ray scattering) analysis of a surface having a wetting angle of about 5 degrees with respect to purified water at room temperature according to the above method. Figure 17 is a graph showing the results of a GISAXS (grazing angle incident small angle X-ray scattering) analysis of a surface having a wetting angle of about 60 degrees with respect to purified water (as a hydrophobic surface) at room temperature according to the above method. The in-plane phase diffraction pattern was confirmed in any of the examples, and the block copolymer of Example 1 had a vertical alignment property.

Further, block copolymers having different volume fractions were prepared in the same manner as in Example 1, except for controlling the molar ratio of the monomer and the macroinitiator.

The volume fraction is as follows.

The volume fraction of each block of the block copolymer is calculated based on the molecular weight measured by GPC (gel permeation chromatography) and the density at room temperature. In the above, the density is measured by a buoyancy method, in particular, by mass of a block copolymer of mass and density known in air in a solvent such as ethanol, and GPC is carried out according to the above method. The results of the GISAXS analysis for each sample are illustrated in Figures 18-20. 18 to 20 are the results regarding the samples 1 to 3, respectively, and the in-plane phase diffraction pattern of the GISAXS can be observed from the figure confirmation, and from this it can be predicted to have the vertical alignment property.

Test Example 3

It was confirmed from Test Example 1 that the block copolymer in the examples had substantially excellent self-assembly properties. In the examples, surface energy and density were evaluated with respect to Comparative Example 1 and Examples 1 to 5 and 13, in which commensurate results were observed.

The surface energy was measured using a drop shape analyzer (DSA 100 product from KRUSS, Co.). The surface energy is evaluated by a polymer layer formed by spin coating a coating solution prepared by dissolving the material to be evaluated in fluorobenzene so as to have a solid content of 2% by weight. Rounded so that the coating has a thickness of 50 nm (coating area: width = 2 cm, length = 2 cm), and the layer is allowed to dry at room temperature for about 1 hour, and then the layer is allowed to stand at about Thermal annealing at 160 ° C for about 1 hour. The surface energy was calculated from the average calculated by the average of the measured liquids of two known surface tensions, deionized water (H ₂ O) and diiodomethane, respectively. In the table below, the surface energy of each block is based on the surface energy measured by the above method for the homopolymer formed from the monomers forming the corresponding block.

The method of measuring the density is the same as the above.

The measurement results are stated in the table below.

From the above table, it can be confirmed that there is a particular tendency in the examples in which the appropriate self-assembly properties are confirmed (Examples 1 to 5). Specifically, in the block copolymers of Examples 1 to 5, the absolute value of the difference between the surface energies of the first and second blocks is from 2.5 millinewtons/meter to 7 millinewtons/meter. Within the range; however, Example 13 and Comparative Example 1 show that the absolute value of the difference between the surface energies does not fall within the above range. Again, the first block exhibits a higher surface energy than the second block and ranges from 20 millinewtons per meter to 35 millinewtons per meter. Further, the absolute difference between the densities of the first and second blocks of the block copolymers of Examples 1 to 5 was 0.3 g/li. Square centimeters or larger.

Test Example 4

The results of XRD analysis of Comparative Example 1 and Examples 1 to 5 and 13 in which commensurate results were observed are exemplified in Table 4 below.

The XRD pattern is evaluated by measuring the scattering intensity from the scattering vector (q) by passing X-rays through a sample in the 3C beam path of the Pohang Light Source. After the sample was placed in a bath for measuring XRD, a powder obtained without performing any specific pretreated block copolymer for purifying impurities was used as a sample. During the XRD pattern analysis, X-rays having a vertical size of 0.023 mm and a horizontal size of 0.3 mm were used as X-rays, and a measuring device (for example, 2D marCCD) was used as a detector. A 2D diffraction pattern that is image-scattered from the sample is obtained, and the obtained diffraction pattern is calibrated into a scattering vector (q) by using silver behenate, and then cyclically averaged, and then plotted according to the scattering vector (q) For scattering intensity. The position of the peak and the FWHM are obtained by plotting the scattering intensity and peak fit from the scattering vector (q). From the above results, it was confirmed that the block copolymer exhibiting excellent self-assembly properties exhibited a specific XRD pattern as compared with the comparative example in which the self-assembly property was not confirmed. Certain words, FWHM of the peak in the range of 0.2 nm ^-1 to 1.5 nm ^-1 to a peak of 0.5 nm was observed from the scattering vector range of ¹ to 10 nm ^-1 in the; however, not These peaks were observed in Example 13 and Comparative Example 1.

Claims (21)

A block copolymer comprising a block represented by the following formula 4: Wherein R is hydrogen or alkyl, X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkyl group, an alkenyl group, an alkynyl 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 extended alkenyl group or an alkynylene group, and Y is contained and A monovalent substituent having an aromatic structure of at least 3 linearly linked atoms forming a chain or a monovalent substituent comprising an alicyclic structure linked to a chain having 8 or more chains forming an atom. A block copolymer according to the first aspect of the invention, wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. The block copolymer according to claim 1, wherein X is a single bond, an oxygen atom, -C(=O)-O- or -O-C(=O)-. A block copolymer according to the first aspect of the invention, wherein X is -C(=O)-O-. The block copolymer according to claim 1, wherein the chain bonded to the aromatic or aliphatic cyclic structure contains 8 to 20 chain-forming atoms. a block copolymer according to claim 1 of the scope of the patent application, wherein The atoms forming the chain are carbon, oxygen or nitrogen. The block copolymer according to claim 1, wherein the chain is a hydrocarbon chain. The block copolymer according to claim 1, wherein the chain is directly bonded to the aromatic structure or the aliphatic ring structure, or the chain is linked to the aromatic structure or the fat via a linker Ring structure. The block copolymer according to claim 8 wherein the linking group is an oxygen atom, a sulfur atom, -NR ₃ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group. Wherein R ₃ is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl. The block copolymer according to claim 1, wherein the aromatic structure contains 6 to 12 carbon atoms, and the alicyclic structure contains 3 to 12 carbon atoms. According to the block copolymer of the first aspect of the patent application, Y is represented by the following formula 2: [Formula 2] -PQZ wherein P is an extended aryl group or a cycloalkyl group, and 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 a chain having 3 or more chain-forming atoms in the case where P is an extended aryl group, Or in the case where P is a cycloalkyl group, the chain having 8 or more chain-forming atoms. According to the patent application range block copolymer, Paragraph 1, wherein when the X-ray diffraction analysis, it exhibits from 0.5 nm to 10 nm ^-1 Q ^-1 of the value range of the FWHM (full width at half maximum) peak in the range of 0.2 nm ^-1 to 1.5 nm ^-1 is from the. The block copolymer according to claim 1, wherein the ratio of the number of atoms forming the chain (n) to the distance between the blocks in the self-assembled state (D, unit: nanometer) (n / D) of from 2.5 nm to 5 nm ^{-1 -1.} The block copolymer according to claim 1, wherein the block represented by Formula 4 has a volume fraction ranging from 0.4 to 0.8. The block copolymer according to claim 1, further comprising a second block, the absolute value of the difference between the surface energy of the block represented by Formula 4 and the second block being from 2.5 millinewtons / metric to 7 millinewtons / meter range. The block copolymer according to claim 15 wherein the block represented by Formula 4 has a higher surface energy than the second block. The block copolymer according to the first aspect of the patent application, wherein the surface energy of the block represented by Formula 4 is in a range from 20 millinewtons/meter to 35 millinewtons/meter. The block copolymer according to claim 1, further comprising a second block, wherein the difference between the density of the block represented by Formula 4 and the density of the second block is 0.3 g/cm 3 or Bigger. A polymer layer comprising the self-assembled product of the block copolymer of claim 1 of the patent. A method for forming a polymer layer comprising forming a inclusion The polymer layer of the self-assembled product of the block copolymer of claim 1 of the patent application. A pattern forming method comprising selectively removing a block copolymer from a laminate comprising a substrate and a polymer layer formed on the substrate and comprising a self-assembled product of the block copolymer of claim 1 The block represented by Formula 4 or a block different from the block represented by Formula 4.