TWI596128B - Block copolymer - Google Patents

Description

Block copolymer

This application is directed to a block copolymer.

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

This application provides block copolymers and their use.

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

The term "alkoxy" as used herein, unless otherwise defined, may refer to an alkoxy 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. The alkoxy group may have a linear, branched, or cyclic structure, and may be optionally substituted with at least one substituent.

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

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

As used herein, unless otherwise defined, the term "aryl or extended aryl" may be taken from, or include, a compound comprising a benzene ring structure. A monovalent or divalent substituent derived from a compound having at least two benzene rings bonded by a shared one or two carbon atoms or by a random linker, or a derivative of the compound. The term aryl or extended aryl, unless otherwise defined, may be an aryl group having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms.

The term "aromatic structure" as used herein may refer to the aryl or extended aryl group.

As used herein, the term "alicyclic structure", unless otherwise defined, may refer to a cyclic hydrocarbon structure of a non-aromatic cyclic structure. The alicyclic structure, unless otherwise defined, may be a structure having 3 to 30, 3 to 25, 3 to 21, 3 to 18, or 3 to 13 carbon atoms.

As used herein, "single bond" can refer to the absence of an atom at the corresponding position. For example, the case where "B" in the structure shown by "A-B-C" is a single bond means that the "B" position has no atom and thus is directly connected to "C" by "A" to form a structure represented by "A-C".

The substituent which may be optionally 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 or a halogen. Atom, carboxyl group, epoxypropyl group, propylene fluorenyl group, methacryl fluorenyl group, acryloxy group, methacryloxy group, thio group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenyl group And an alkynyl group, an alkoxy group or an aryl group, but is not limited thereto.

In one embodiment, a monomer of the following formula 1 having a novel structure and capable of forming a block copolymer is provided.

In Formula 1, R is hydrogen or an alkyl group, 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, and -C(=O). ) -X ₁ - or -X ₁ -C(=O)-. Wherein 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 a chain linkage comprising 8 or more chain-forming atoms. A monovalent substituent of the cyclic structure.

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 not limited to this.

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

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

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 case, 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 of the alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted with another substituent.

In Formula 1, Y may include a cyclic structure. The chain can be attached to a ring structure. The self-assembly of the block copolymer formed of the compound can be further improved by the cyclic structure. The cyclic structure may be an aromatic structure or an alicyclic structure.

The chain can be attached directly to the ring structure or can be attached to the ring structure via a linker. As an example of the linker, an oxygen atom, a sulfur atom, -NR ₁ -, -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 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 alkyl, alkenyl or alkynyl group, wherein R ₂ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl. A suitable linker can be an oxygen atom or a nitrogen atom. For example, a chain can be attached to an aromatic structure via an oxygen or nitrogen atom. In this case, the linker may be an oxygen atom or -NR ₁ -, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl.

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

[Formula 2]-P-Q-Z

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 having at least 8 chain-forming atoms. In the case where 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.

As a suitable embodiment of the monomer of Formula 1, it is exemplified that R in the monomer of Formula 1 is a hydrogen atom or an alkyl group; or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is - C(=O)-O- and Y is a substituent of the formula 2, wherein P is an extended aryl group having 6 to 12 carbon atoms or a phenyl group, Q is an oxygen atom and Z is 8 or more A chain of chains of atoms.

Therefore, as a suitable embodiment, for example, the monomer of the following formula 3 can be used.

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 an oxygen atom. Z is the aforementioned chain having 8 or more chain-forming atoms.

Another embodiment of the present application is directed to a method of making a block copolymer comprising the step of forming a block by polymerization of a monomer.

The specific method of 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 aforementioned monomer.

For example, a block copolymer can be produced using a monomer by living radical polymerization (LRP). For example, the method is, for example, an anionic polymerization in which a block copolymer is synthesized in the presence of a mineral acid salt such as an alkali metal salt or an alkaline earth metal salt, and an organic rare earth metal complex or an organic alkali metal compound is used as a polymerization reaction. An initiator polymerization method in which a block copolymer is synthesized in the presence of an organoaluminum compound, which uses an organic alkali metal compound as a polymerization initiator; atom transfer radical polymerization (ATRP), which uses atom transfer radicals a polymerization agent as a polymerization reaction agent; an ATRP of an electron transfer regeneration activator (ATGET), using an atom transfer radical polymerization agent as a polymerization reaction controlling agent in the presence of an electron-generating organic or inorganic reducing agent for polymerization; Initiator continuous regenerating activator (ICAR) ATRP; reversible addition-open chain transfer (RAFT) polymerization using an inorganic reducing agent reversible addition-opening chain transfer agent; and using an organic ruthenium compound as an initiator The method, the appropriate method may be selected from the above methods.

In one embodiment, the method of making a block copolymer can A material comprising a monomer capable of forming a block is polymerized by living radical polymerization in the presence of a radical initiator and a living radical polymerization agent.

In the manufacture of the block copolymer, a method for forming other blocks included in the block copolymer and a block formed by the above monomers are not particularly limited, and the other blocks can be considered by formation The block species are formed by selecting an appropriate monomer.

The method of producing a block copolymer may further comprise precipitating a polymerization product obtained by the foregoing method in a non-solvent.

The type 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'- even bis-(2, 4-dimethylvaleronitrile)), or a peroxide compound (such as benzalkonium peroxide (BPO) or di-tertiary butyl peroxide (DTBP))

LRP can be used in solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, It is carried out in 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-gum) can be used without limitation. Alkane or petroleum ether).

Another embodiment of the present application is related to A block copolymer of a block formed by a monomer (hereinafter, may be referred to as a first block).

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

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

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 alkyl group, or a stretch. Alkenyl, alkynyl, -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 comprising a chain-linked cyclic structure having 8 or more chain-forming atoms. As for the specific kind of each of the above substituents, the foregoing description can be applied in the same manner.

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 alkyl group having from 1 to 4 carbon atoms, and X is -C(=O) -O-, Y is a substituent represented by Formula 2. This 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 may be Is 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 is a chain atom having 8 or more Chain. 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. This first block can 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, S(=O) ₂ -, alkylene, 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 a chain having at least 8 chain atoms .

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

As a special embodiment of the chain Y in the 1B block, the above description about the formula 1 can be applied to the same in a similar manner.

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 chain atoms having 8 or more chains of chain atoms is negative. The electrical property is 3 or higher. In another embodiment, the zetaelectricity of the chain-forming atoms may be 3.7 or less. Here, this block can be referred to as a 1C block. An example of the atom having an anion of 3 or more may be a nitrogen atom or an oxygen atom, but is not limited thereto.

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

For example, the second block may be a polyvinylpyrrolidone block, a polylactic acid block, a polyvinylpyridine block, a polystyrene block (such as a polystyrene block or 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). The block 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 (eg, 1A, 1B or 1C block) can be a package A block comprising an aromatic structure comprising at least one halogen atom.

This second block can be represented, for example, by the following formula 7 and can 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.

This second block can effectively interact with the aforementioned first block, so that the block copolymer has excellent self-assembly characteristics.

The aromatic structure of Formula 7 may be, for example, an aromatic structure having 6 to 18 or 6 to 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 suitably a fluorine atom.

In one embodiment, B of Formula 7 may be a monovalent substituent having an aromatic structure having 6 to 12 carbon atoms, which may be 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 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 is a An aryl group substituted with at least one halogen atom. Above, 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 halogen atoms Substituted aryl.

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 extended 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 another embodiment, 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 (e.g., 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 of formula 10. This block 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 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 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 still another embodiment, the 2C block can be a block of Formula 10, and both T and K in 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 still another embodiment, the second block can be a block comprising at least one metal atom or a metalloid atom. This block can be referred to as a 2D block. This block can improve the etch selectivity when the etching process is performed, for example, with a film comprising a self-assembled block copolymer.

The metal atom or metalloid atom in the 2D block may be a ruthenium atom, an iron atom or a boron atom, but is not particularly limited as long as it exhibits appropriate etch selectivity due to a difference from another atom in the block copolymer. Just fine.

The 2D block may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms, for example, a fluorine atom, and a metal or metalloid 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 can be from 6 to 12 carbon atoms An aromatic structure, for example, 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 -, an alkylene group, an alkenyl group or an alkynyl group, and W may be an aryl group including at least one halogen atom and a substituent including a metal atom or a metalloid atom.

Wherein W may be an aryl group having 6 to 12 carbon atoms and including at least one halogen atom and a substituent containing a metal atom or a metalloid atom.

The aryl group may include at least one or 1 to 3 substituents containing a metal atom or a metalloid-like atom, and 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen 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 R ₁ to R ₅ may each independently be hydrogen, an alkyl group, a haloalkyl group or a halogen atom. Or a substituent including a metal or metalloid atom, provided that at least one of R ₁ to R ₅ includes a hydrogen atom, and at least one of R ₁ to R ₅ includes a substituent of a metal or a metalloid atom.

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

In Formula 13, 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. 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 aforementioned substituent including a metal or metalloid atom may be a carboranyl group or a sesquiphenyloxyalkyl group. (silsesquioxanyl group) (such as polyhedral oligomeric sesquioxanes), ferrocene or trialkyl decyloxy. However, it is not particularly limited as long as it is selected to obtain etching selectivity by including at least one metal or metalloid atom.

In still another embodiment, the second block may be a block including an atom having an anion of 3 or more and a non-halogen atom (hereinafter referred to as a non-halogen atom). This block can be referred to as a 2E block. In another embodiment, the non-halogen atom in the 2E block may have a cathode electrical conductivity 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 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms, except for a non-halogen atom having an anion of 3 or more. For example, a fluorine atom. The number of halogen atoms (e.g., 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 the formula 14.

In Formula 14, B may be a monovalent substituent having an aromatic structure including a substituent including 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, for example, an aryl group or an aryl group.

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

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 or a sulfur atom , -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, and W may be an aryl group, including a non-halogen containing an electronegativity of 3 or higher a substituent of an atom and at least one halogen atom.

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

The aryl group may include at least one or 1 to 3 substituents including a non-halogen atom having an anion of 3 or more. Further, this aryl group may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. Wherein 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, -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 or a sulfur atom And -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, and R ₁ to R ₅ may each independently be hydrogen, alkyl, haloalkyl, halogen atom and A substituent containing a non-halogen atom having an anion of 3 or higher. Wherein at least one of R ₁ to R ₅ is a halogen atom, and at least one of R ₁ to R ₅ is a substituent containing a non-halogen atom having an anion of 3 or more.

In Formula 16, at least one of R ₁ to R ₅ , 1 to 3, or 1 to 2 may be a substituent of the aforementioned non-halogen atom having an anion 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 foregoing includes a non-halogen atom having an anion of 3 or higher. The substituent may be, but not limited to, a hydroxyl group, an alkoxy group, a carboxyl group, a decylamino group, an ethoxylated 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. This second block can 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 as needed.

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, -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 or a sulfur atom And -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, 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 the 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, sulfur An atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and R ₁ to R ₅ may each independently be hydrogen, an alkyl group, a haloalkyl group or a halogen atom. Or a heterocyclic substituent. Wherein 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 others may be a hydrogen atom, an alkyl group or a halogen atom; or a hydrogen atom or a halogen An 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 thiophene, a substituent derived from a thiazole, a substituent derived from a carbazole or a substituent derived from imidazole. .

The block copolymer of the present application may comprise at least one of the above first blocks and at least one of the above second blocks. This block copolymer 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.

This block copolymer can exhibit substantially excellent self-assembly or phase separation properties. Furthermore, self-assembly or phase separation properties may be further improved if block selection and combination are made such that the block copolymer meets at least one of the parameters described below.

Since the block copolymer contains two or more polymer chains connected to each other via a covalent bond, it can be phase-separated. The block copolymers of the present application exhibit excellent phase separation properties which, if desired, can be formed by microphase separation to form a nano-sized structure. The shape or size of the nano-sized structure can be controlled by the size (molecular weight, etc.) of the block copolymer or the relative proportion of the block. The structure formed by phase separation may include a sphere, a cylinder, a spiral tetrahedron, and a laminate and a reversed structure, and the ability to form the foregoing structure may be referred to as self-assembly. The inventors of the present invention have confirmed that among the above various block copolymers having various structures, the block copolymer satisfying at least one of the following parameters can exhibit further improved self-assembly property of the block copolymer. This block copolymer conforms to one of the parameters described below or two or more of the following descriptions. In particular, it was confirmed that the block copolymer can exhibit an upright alignment property by satisfying the block copolymer with appropriate parameters. As used herein, "upright alignment properties" refers to the alignment properties of the block copolymer and may refer to the nano-sized structures formed by the block copolymers aligned in a direction perpendicular to the substrate. The self-assembled structure of the block copolymer is a practical application for controlling the block copolymer of the technical system which is upright or parallel to various substrates. A big focus. Conventionally, the arrangement of the nano-sized structures in the layers of the block copolymer depends on the block in the surface or air in the block forming the block copolymer. Generally, since many substrates are polar and air is non-polar, blocks that are more polar than other blocks in the block copolymer are wet on the substrate and are less polar than other in-block copolymers. The block of the segment is wetted at the interface between the air. Accordingly, a number of techniques have been proposed to simultaneously wet the substrate while the blocks of different properties in the block copolymer are simultaneously wetted, and the most common method is to control the alignment by fabricating a neutral surface. However, in one embodiment, the block copolymer can be aligned perpendicular to the substrate by controlling the following parameters, without the usual processing to achieve upright alignment, including neutral surface treatment. In addition, in another embodiment, by the thermal annealing, the vertical alignment is completed in a short time in a large area.

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

As used herein, the term "in-plane phase diffraction pattern exhibiting grazing angle incident small angle X-ray scattering (GISAXS)" may mean that a peak perpendicular to the X coordinate is observed in the GISAXS diffraction pattern when performing GISAXS analysis. Happening. This peak can be confirmed by the upright alignment property of the block copolymer. Therefore, a block copolymer exhibiting an in-plane phase diffraction pattern exhibits an upright alignment property. In a further embodiment, two or more peaks are observed at the X coordinate of the GISAXS diffraction pattern. In view In the case where two or more peaks were observed, it was confirmed that the scattering vector (q value) has a fixed ratio, and in the above case, the phase separation efficiency can be further improved.

As used herein, the term "vertical" is a vocabulary that takes into account errors, for example, which may include errors within ±10 degrees, ±8 degrees, ±6 degrees, ±4 degrees, or ±2 degrees.

Block copolymers capable of forming a layer exhibiting an in-plane phase diffraction pattern on both hydrophobic and hydrophilic surfaces can exhibit upright alignment properties on various surfaces that are not subjected to any treatment that induces upright alignment. As used herein, the term "hydrophobic surface" may refer to a surface having a wetting angle of pure water ranging from 5 degrees to 20 degrees. Examples of the hydrophobic surface may include a polyfluorinated surface treated with a piranha solution, sulfuric acid, or an oxygen plasma, but are not limited thereto. As used herein, the term "hydrophilic surface" may refer to a surface having a wetting angle of pure water ranging from 50 degrees to 70 degrees. Examples of the hydrophilic surface may include a hydrogen fluoride-treated polyoxonium surface, hexamethyldiazane-treated polyfluorene oxide or oxygen plasma-treated polydimethylsiloxane, but are not limited thereto.

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

The layer formed on the hydrophobic or hydrophilic surface and exhibiting the in-plane phase diffraction pattern on the GISAXS may be a thermally annealed layer. In one embodiment, the layer for determining GISAXS is, for example, a coating solution prepared by diluting a block copolymer in a solvent (for example, fluorobenzene) to a concentration of about 0.7% by weight. The coating was prepared on a corresponding hydrophobic or hydrophilic surface such that the coating had a thickness of about 25 nm and an area of about 2.25 cm ² (width: 1.5 cm, length: 1.5 cm) and then thermal annealing. This 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 such that its incident angle is in the range of 0.12 to 0.23 degrees. A diffraction pattern scattered from the layer can be obtained by a conventional measuring device (for example, 2D marCCD). Techniques for confirming the presence of an in-plane phase diffraction pattern from the diffraction pattern obtained above are known in the art.

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

At the X-ray diffraction (XRD) analysis, the block copolymer exhibits at least one peak in some range of the scattering vector (q value).

In one embodiment, at the time of XRD, the block copolymer exhibits at least one peak in the range of 0.5 nm ^-1 to 10 nm ^{-1 of the} scattering vector (q value). Other aspects of the embodiments, the at least 1.3nm ^-1 was observed a peak scattering vector (q value) may range 0.7nm ^-1 or greater, 0.9nm ^-1 or greater, 1.1nm ^-1 or higher, or more High, or 1.5nm ^-1 or higher. In other embodiments, it is observed that the scattering vector (q value) of at least one peak may range from 9 nm ^-1 or lower, 8 nm ^-1 or lower, 7 nm ^-1 or lower, 6 nm ^-1 or lower, 5 nm ^{- 1} or lower, 4 nm ^-1 or lower, 3.5 nm ^-1 or lower, or 3 nm ^-1 or lower.

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

As used herein, "FWHM" refers to the width of the peak (the difference between the scattering vectors (q's) at a position where the intensity is half of the maximum intensity.

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

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

XRD analysis can be performed by passing X-rays through a block copolymer sample and measuring the scattering intensity from the scattering vector. Can be without any The specifically pretreated block copolymer is subjected to XRD analysis, and, for example, XRD analysis can be performed by passing X-rays through the block copolymer after drying under appropriate conditions. As the X-ray person, X-rays having a vertical size of 0.023 mm and a horizontal size of 0.3 mm can be used. An image of the 2D diffraction pattern scattered from the sample is obtained by using a measuring device (for example, 2D marCCD), and then the resulting diffraction pattern is subjected to the above fitting to obtain a scattering vector, FWHM, and the like.

As described below, in the case where at least one block of the block copolymer includes a chain, the number of chain-forming atoms (n) and the scattering vector (q) obtained from XRD analysis conform to Equation 1 below.

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

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

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

The scattering value substituted into the value of Equation 1 may be a scattering value in the range of 0.5 nm ^-1 to 10 nm ^-1 . In another embodiment, the scattering value substituted into the value of Equation 1 may be 0.7 nm ^-1 or higher, 0.9 nm ^-1 or higher, 1.1 nm ^-1 or higher, 1.3 nm ^-1 or higher, Or 1.5nm ^-1 or higher. In another embodiment, the scattering value substituted into the value of Equation 1 may be 9 nm ^-1 or lower, 8 nm ^-1 or lower, 7 nm ^-1 or lower, 6 nm ^-1 or lower, 5 nm ^-1 or Lower, 4 nm ^-1 or lower, 3.5 nm ^-1 or lower, or 3 nm ^-1 or lower.

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

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

The surface energy can be measured by using a droplet shape analyzer (DSA100 product, manufactured by KRUSS, Co.). In particular, a coating liquid prepared by diluting a sample (block copolymer or homopolymer) to be determined in fluorobenzene to a solid content of about 2% by weight can be applied to a substrate. The coating layer was allowed to have a thickness of 50 nm and a coating area of 4 cm ² (width: 2 cm, length: 2 cm); the coating was dried at room temperature for about 1 hour; and then thermally annealed at 160 ° C for about 1 hour to obtain a layer. Surface energy measurement was performed. After the layer was thermally annealed, deionized water of known surface tension was dropped and the contact angle was measured thereafter. The above method for obtaining the contact angle of deionized water was repeated five times, and the average value of the obtained contact angles was calculated five times. Similarly, on the layer which has been thermally annealed, diiodomethane whose surface tension is known is dropped and the contact angle is measured thereafter. The above method for obtaining the contact angle of diiodomethane was repeated five times, and the average value of the obtained contact angles was calculated five times. Thereafter, the average value obtained by the contact angle of deionized water and diiodotoluene was used by the Owens-Wendt-Rabel-Kaelble method to obtain the surface energy by substituting the value (Strom value) with respect to the surface tension of the solvent. By using the above method, the surface energy of each block in the block copolymer can be obtained by forming a homopolymer obtained from the monomer of the corresponding block.

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

In the block copolymer, the difference between the densities of the first and second blocks may be 0.25 g/cm ³ or higher, 0.3 g/cm ³ or higher, 0.35 g/cm ³ or higher. 0.4 g/cm ³ or higher, or 0.45 g/cm ³ or higher. The absolute value of the difference between the densities may be 0.9 g/cm ³ or less, 0.8 g/cm ³ or less, 0.7 g/cm ³ or less, 0.65 g/cm ³ or less, or 0.6 g/cm. ³ or lower. The absolute value of the difference between the densities of the first and second block blocks is connected via a covalent bond in the above range, and effective microphase separation can be achieved by phase separation by appropriate incompatibility.

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

In the case where the block copolymer contains the above chain, the density of the block containing the chain is lower than that of the other blocks. For example, if the first block comprises the chain, the density of the first block is lower than the second block. In this case, the density of the first block may range from about 0.9 g/cm ³ to about 1.5 g/cm ³ . In another embodiment, the first block may have a density of about 0.95 g/cm ³ or higher. The first block may have a density of about 1.4 g/cm ³ or less, about 1.3 g/cm ³ or less, about 1.2 g/cm ³ or less, about 1.1 g/cm ³ or less, or about 1.05 g/cm ³ or less. The block copolymer including the above first block and exhibiting a difference in density between the above blocks can exhibit excellent self-assembly. Surface energy and density were determined at room temperature.

The block copolymer may include a block having a volume fraction of from 0.4 to 0.8 and a block having a volume fraction of from 0.2 to 0.6. In the block copolymer In the case of a chain, the block having the chain may have a volume fraction of 0.4 to 0.8. For example, the first block comprises the chain, the first block may have a volume fraction of 0.4 to 0.8 and the second block may have a volume fraction of 0.2 to 0.6. The sum of the volume fractions of the first and second blocks is 1. The block copolymers of the respective blocks included in the above volume fraction can exhibit excellent self-assembly. The volume fraction of each block of the block copolymer can be obtained by using the density of each block and the molecular weight obtained by gel permeation chromatography (GPC).

The block copolymer may have, for example, a number average molecular weight (Mn) in the range of from about 3,000 to 300,000. As used herein, "number average molecular weight" means a value measured by GPC (gel permeation chromatography) relative to a polystyrene standard. As used herein, unless otherwise indicated, "molecular weight" as used herein refers to a number average molecular weight. In another embodiment, the molecular weight (Mn) may be, for example, 3000 or higher, 5000 or higher, 7000 or higher, 9000 or higher, 11,000 or higher, 13,000 or higher, or 15,000 or more. high. In another embodiment, the molecular weight (Mn) may be, for example, 250,000 or less, 200,000 or less, 180,000 or less, 160,000 or less, 140,000 or less, 120,000 or less, 100,000 or more. Low, 90,000 or lower, 80,000 or lower, 70,000 or lower, 60,000 or lower, 50,000 or lower, 40,000 or lower, 30,000 or lower, or 25,000 or lower. The block copolymer may have a polydispersity (Mw/Mn) in the range of 1.01 to 1.60. In another embodiment, the polydispersity can be about 1.1 or higher, about 1.2 or higher, about 1.3 or higher, or about 1.4 or higher.

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

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

This application is directed to a polymer layer comprising a block copolymer. This polymer layer can be used in a variety of applications. For example, it can be used for a biosensor, a recording medium (such as a flash memory), a magnetic storage medium or a pattern forming method, or a power device or an electronic device.

In one embodiment, the block copolymer in the polymer layer can be self-assembled to form a periodic structure, including a sphere, a cylinder, a helix, a tetrahedron, or a layer.

For example, in a block copolymer, a first block or a second block or other block is linked to one segment of the above block via a covalent bond, and other segments may form a regular structure, such as a laminated form, Cylindrical form, etc.

The polymer layer can exhibit the above-described in-phase phase diffraction pattern, that is, a peak perpendicular to the X coordinate in the GISAXS diffraction pattern of the GISAXS analysis. In a further embodiment, two or more peaks are observed at the X coordinate of the GISAXS diffraction pattern. In the case where two or more peaks are observed, it can be confirmed that the scattering vector (q value) has a fixed ratio.

This application is also directed to a method of forming a polymer layer using a block copolymer. The method includes forming a polymer layer comprising a block copolymer in a self-assembled state on a substrate. For example, the method includes forming a block copolymer or a coating liquid on a substrate by coating or the like (wherein the block copolymer is suitable The layer is diluted in the solvent, and the layer is aged or heat treated as needed.

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

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

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

For example, according to this method, a nano-size pattern having a high aspect ratio of cerium oxide can be formed. For example, a state in which a polymer layer is formed on ruthenium oxide and a block copolymer in a polymer layer is formed in a predetermined structure Selectively removing any of the blocks of the block copolymer and etching the yttrium oxide in various ways (eg, reactive ion etching) can form various types of patterns (eg, nanorods or nanopores). pattern). Further, according to the above method, a nano pattern having a high aspect ratio can be formed.

For example, the formed pattern size may be several tens of nanometers, and the pattern can be used for various purposes, including next generation information electronic magnetic recording media.

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

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

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

Further, after the ultraviolet ray irradiation, the polymer layer is subjected to an acid treatment to further remove the segment broken by the ultraviolet rays.

Further, an etching treatment is performed on a substrate using a polymer layer (selectively removing the block from the same), which can be performed by reactive ion etching using CF ₄ /Ar ions, and after the above procedure, further The polymer layer is removed from the substrate by oxygen plasma treatment.

This application provides block copolymers and their use. The block copolymer has excellent self-assembly and phase separation, and various desired functions can be freely imparted to it when necessary.

Figures 1 through 20 are SEM or AFM images of the polymer layer and are presented as a result of a GISAXS analysis of the polymer layer.

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

NMR analysis

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

<abbreviation>

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

2. GPC (gel permeation chromatography)

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

<GPC measurement conditions>

Device: Agilent technologies, Co.'s 1200 Series

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

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1mg/mL, injection 200L

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

Preparation Example 1

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

<Results of NMR analysis of intermediate products>

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

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

<NMR 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)

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

<NMR Results of DPM-C8>

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

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

<NMR Results of DPM-C10>

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

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

<NMR Results of DPM-C14>

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

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

<NMR Results of DPM-C16>

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

Wherein 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. In a 500 mL bottle, Pd/C (palladium on carbon) (1.13 g, 1.06 mmole) and 200 mL of 2-propanol were added, followed by ammonium formate dissolved in 20 mL of water, followed by reaction at room temperature. Pd/C was activated in 1 minute. Thereafter, 4-aminophenol (1.15 g, 10.6 mmole) and lauric aldehyde (1.95 g, 10.6 mmole) were added thereto, and the mixture was stirred at room temperature for 1 minute by stirring under nitrogen. After the reaction, Pd/C was removed and 2-propanol for the reaction was removed, after which the mixture was extracted with water and dichloromethane to remove unreacted product. The organic layer was collected and dehydrated over MgSO _4. The crude product was purified by column chromatography (mobile phase: hexane/ethyl acetate) to afford colourless solid intermediate (1.98 g, 7.1 mmole) (yield: 67%).

<Results of NMR analysis of intermediate products>

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)

Synthetic intermediate (1.98 g, 7.1 mmole), methyl Acrylic acid (0.92 g, 10.7 mmole), dicyclohexylcarbodiimide (DCC; 2.21 g, 10.7 mmole) and p-dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmole) were placed in a bottle, and 100 ml of two were added. Methyl chloride was reacted under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt obtained during the reaction was removed by a filter, and the remaining dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as a mobile phase, and the obtained product was recrystallized from a mixed solvent of methanol and water (methanol: water = 3:1 (weight ratio)). This gave the product as a white solid (DPM-N2) (1.94 g, 5.6 mmole).

<NMR Results of 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)

Wherein R is a linear alkyl group having 12 carbon atoms.

Preparation Example 7

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

<NMR Results of DPM-C4>

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

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

0.3 g of macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mL of benzene were added to a 10 mL Schlenk bottle, followed by stirring at room temperature for 30 minutes, followed by RAFT for 4 hours at 115 ° C (reversible addition) Splitting chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to give a pale pink block copolymer. The yield of this block copolymer was about 18%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 16,300 and 1.13, respectively. This block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from pentafluorostyrene.

Example 2

A block copolymer was prepared by the same method as in Example 1, except that the macroinitiator prepared by substituting the compound of Preparation Example 2 (DPM-C8) in place of the compound of Preparation Example 1 (DPM-C12) and using five Fluorostyrene. This 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 by the same method as in Example 1, except that the macroinitiator prepared by substituting the compound of Preparation Example 3 (DPM-C10) in place of the compound of Preparation Example 1 (DPM-C12) and using five Fluorostyrene. This 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

Block copolymerization was carried out by the same method as in Example 1. However, a macroinitiator prepared by substituting the compound of Preparation Example 4 (DPM-C14) in place of the compound of Preparation Example 1 (DPM-C12) was used, and pentafluorostyrene was used. This 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

A block copolymer was prepared by the same method as in Example 1, except that the macroinitiator prepared by substituting the compound of Preparation Example 5 (DPM-C16) in place of the compound of Preparation Example 1 (DPM-C12) and using five Fluorostyrene. This 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 mmole) was added to a mixed solution of 400 mL of tertiary butanol and potassium hydroxide (37.5 g, 161 mmole); followed by a reflux reaction for 2 hours. After the reaction, the product was cooled to room temperature, and 1200 mL of water was added, and the remaining butanol used in the reaction was volatilized. The adduct was extracted three times with diethyl ether (300 mL) and the aqueous phase was acidified with a 10% by weight hydrochloric acid solution until its pH became 3, whereby the title product was precipitated. The precipitated product was extracted three times with diethyl ether (300 mL) and organic layer was collected. The organic layer was dried over MgSO ₄ and the solvent was removed. The crude product was purified by column chromatography using hexanes and DCM (dichloromethane) as a mobile phase, whereby colorless liquid 3-hydroxy-1,2,4,5-tetrafluorostyrene was obtained. (11.4g). 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

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition split-chain transfer) agent (2-cyano-2-propyldodecyl trithiocarbonate) and the compound of Preparation Example 1 (DPM -C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent: AIBN) (concentration: 70% by weight), and then obtained by reacting the mixture under nitrogen at 70 ° C for 4 hours. Macromolecular initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Thereafter, in benzene, the synthesized macroinitiator, 3-hydroxy-1,2,4,5-tetrafluorostyrene (TFS-OH) and AIBN (azobisisobutyronitrile) are 1:200:0.5 The weight ratio of the (macromolecule initiator: TFS-OH: AIBN) was dissolved (concentration: 30% by weight), and the mixture was reacted under nitrogen at 70 ° C for 6 hours to obtain a block copolymer (quantitative average molecular weight: 35000, polydispersity: 1.2). This 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 following compound of the formula H was synthesized according to the following method. The quinone imine (10.0 g, 54 mmole) and chloromethylstyrene (8.2 g, 54 mmole) were added to 50 mL of DMF (dimethylformamide) and then reacted under nitrogen at 55 ° C 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, followed by washing with a brine solution. The collected organic layer was treated with MgSO ₄ to remove water, and then the solvent was removed and then recrystallized from pentane to afford compound (11.1 g) as a white solid. 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

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition split-chain transfer) agent (2-cyano-2-propyldodecyl trithiocarbonate) and the compound of Preparation Example 1 (DPM -C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent: AIBN) (concentration: 70% by weight), and then obtained by reacting the mixture under nitrogen at 70 ° C for 4 hours. Macromolecular initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Thereafter, in benzene, the synthesized macroinitiator, the compound of formula H (TFS-PhIM) and AIBN (azobisisobutyronitrile) are 1:200:0.5 (macroinitiator: TFS-PhIM: AIBN) The weight ratio was dissolved (concentration: 30% by weight), and then a block copolymer (quantitative average molecular weight: 35,000, polydispersity: 1.2) was obtained by allowing the mixture to react at 70 ° C for 6 hours under nitrogen. This 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 macroinitiator (Macro-PEO) (poly(ethylene glycol)-4-cyano-4-(phenylsulfonylthiocarbonyl)pentane Poly(ethylene glycol)-4-cyano-4-(phenylcarbonothioylthio)pentanoate, weight average molecular weight: 10,000, sigma aldrich) (the end of the two parts are connected to RAFT (reversible addition splitting chain transfer) reagent), 4.1 mg AIBN (azobisisobutyronitrile) and 3.9 mL of anisole were added to a 10 mL Schlenk bottle and then stirred at room temperature for 30 minutes under nitrogen, followed by 12 hours in a polyoxygenated oil container (70 ° C). RAFT (reversible addition splitting chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to synthesize a pale pink novel block copolymer (number average molecular weight (Mn): 34,300, polydispersity ( Mw/Mn): 1.60). This block copolymer comprises a first block derived from the compound of Preparation Example 1 and a second block of a poly(ethylene oxide) block.

Example 9

2.0 g of the compound of Preparation Example 1 (DPM-C12), 25.5 mg of RAFT (reversible addition split-chain transfer) reagent (cyanoisopropyl dithiobenzoate), 9.4 mg of AIBN (azobisisobutyronitrile) and 5.34 mL benzene was added to a 10 mL Schlenk bottle, stirred at room temperature for 30 minutes, and then in a silicone oil container (70 ° C). Hourly RAFT (reversible addition splitting chain transfer) polymerization. After the polymerization reaction, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to synthesize a pink macromolecule initiator, and the two terminal portions thereof were linked to RAFT (Reversible Addition Splitting Chain Transfer) reagent . The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) were 81.6% by weight, 15400 and 1.16, respectively, 1.177 g of styrene, 0.3 g of the above macroinitiator, and 0.449 mL of benzene to 10 mL. The Schlenk bottle was then stirred at room temperature for 30 minutes, and then subjected to RAFT (reversible addition split-chain transfer) polymerization for 4 hours in a silicone oil container (115 ° C). After the polymerization, the solution of the reaction was precipitated in 250 mL of methanol (which is an extraction solvent), vacuum filtered and dried to synthesize a pale pink novel block copolymer. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) were 39.3% by weight, 31,800 and 1.25, respectively. This block copolymer includes a first block and a polystyrene block (second block) derived from the compound of Preparation Example 1.

Example 10

0.33 g of the macroinitiator synthesized in Example 9, 1.889 g of 4-trimethyldecylstyrene, 2.3 mg of AIBN (azobisisobutyronitrile) and 6.484 mL of benzene added to a 10 mL Schlenk bottle The mixture was then stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT (reversible addition split-chain transfer) polymerization for 24 hours in a silicone oil container (70 ° C). Polymerization Thereafter, the reacted solution was precipitated in 250 mL of methanol which is an extraction solvent, vacuum filtered and dried to synthesize 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. This block copolymer includes a first block derived from the compound of Preparation Example 1 and a poly(4-trimethyldecylstyrene) block (second block).

Example 11 Monomer synthesis

The following compound of formula I was synthesized according to the following procedure. Pentafluorostyrene (25 g, 129 mmole) was added to a mixed solution of 400 mL of tertiary butanol and potassium hydroxide (37.5 g, 161 mmole); followed by a reflux reaction for 2 hours. After the reaction, the product was cooled to room temperature, and 1200 mL of water was added, and the remaining butanol used in the reaction was volatilized. The adduct was extracted three times with diethyl ether (300 mL) and the aqueous phase was acidified with a 10% by weight hydrochloric acid solution until its pH became 3, whereby the title product was precipitated. The precipitated product was extracted three times with diethyl ether (300 mL) and organic layer was collected. The organic layer was dried over MgSO ₄ and the solvent was removed. The crude product was purified by column chromatography using hexanes and DCM (dichloromethane) as a mobile phase to give a colorless liquid intermediate (3-hydroxy-1,2,4,5- Fluorostyrene) (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)

The intermediate product (11.4 g, 59 mmole) was dissolved in DCM (dichloromethane) (250 mL), then imidazole (8.0 g, 118 mmole), DMPA (p-dimethylaminopyridine) (0.29 g, 2.4 mmole) and three Grade butyl chlorodimethyl decane (17.8 g, 118 mmole) was added thereto. The mixture was reacted at room temperature for 24 hours by stirring, and the reaction was stopped by adding 100 mL of brine, followed by additional extraction by DCM. The collected DCM organic layer was dried over MgSO ₄ and solvent was evaporated to afford crude. After purification by column chromatography using hexanes and DCM as a mobile phase, a colourless liquid title product (10.5 g) was obtained. The NMR results of the subject product 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

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition split-chain transfer) agent (2-cyano-2-propyldodecyl trithiocarbonate) and the compound of Preparation Example 1 (DPM -C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent: AIBN) (concentration: 70% by weight), and then obtained by reacting the mixture under nitrogen at 70 ° C for 4 hours. Macromolecular initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Thereafter, in benzene, the synthesized macroinitiator, the compound of formula I (TFS-S) and AIBN (azobisisobutyronitrile) are 1:200:0.5 (macroinitiator: TFS-S: AIBN) The weight ratio was dissolved (concentration: 30% by weight), and then a block copolymer (quantitative average molecular weight: 35,000, polydispersity: 1.2) was obtained by allowing the mixture to react at 70 ° C for 6 hours under nitrogen. This block copolymer comprises a first block derived from the compound of Preparation Example 1 and a second block derived from the compound of formula I.

Example 12

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

Comparative example 1

A block copolymer was prepared by the same method as in Example 1, except that the macroinitiator prepared by substituting the compound of Preparation Example 7 (DPM-C4) in place of the compound of Preparation Example 1 (DPM-C12) and using five Fluorostyrene. This block copolymer includes a first block derived from the compound of Preparation Example 7 (DPM-C4) and a second block derived from pentafluorostyrene.

Comparative example 2

A block copolymer was obtained in the same manner as in Example 1, except that a macromolecular initiator prepared by substituting 4-methoxyphenyl methacrylate for the compound of Preparation Example 1 (DPM-C12) and using five was used. Fluorostyrene. This block copolymer comprises a first block derived from 4-methoxyphenyl methacrylate and a second block derived from pentafluorostyrene.

Comparative example 3

A block copolymer was obtained in the same manner as in Example 1, except that a macroinitiator prepared by substituting the compound of Preparation Example 1 (DPM-C12) with dodecyl methacrylate was used and pentafluorostyrene was used. This block copolymer comprises a first block derived from dodecyl methacrylate and a second block derived from pentafluorostyrene.

Test example 1

A self-assembled polymer layer was obtained by using the block copolymers of Examples 1 to 12 and Comparative Examples 1 to 3 and the results were observed. In other words, 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. Thereafter, self-assembly is performed by solvent annealing or thermal annealing. The solvent used and the aging method are shown in Table 1 below. Thereafter, each polymer layer was subjected to SEM (scanning electron microscope) or AFM (atomic force microscope) analysis to evaluate self-assembly. 1 to 12 are the results of Examples 1 to 12, respectively, and Figs. 13 to 15 are the results of Comparative Examples 1 to 3, respectively.

Test example 2

From Test Example 1, it was confirmed that the block copolymer in the examples had substantially excellent self-assembly. In the examples, the block copolymers produced in Example 1 were evaluated for GISAXS (grazing angle incident small angle X-ray scattering) properties. The above properties are based on the 3C beam of Pohang Light Source. Evaluation in line. The polymer layer is spin-coated on a substrate having a hydrophilic or hydrophobic surface by coating a coating liquid (dissolving the block copolymer of Example 1 in fluorobenzene so that the solid content is 0.7% by weight) The coating layer was formed to have a thickness of 5 nm (coating area: width = 1.5 cm, length = 1.5 cm) and allowed to dry at room temperature for about 1 hour and then subjected to thermal annealing treatment at about 160 ° C for about 1 hour. The formed polymer layer is irradiated with X-rays such that the incident angle is from about 0.12 degrees to 0.23 degrees, which corresponds to an angle between the critical angle of the layer and the critical angle of the substrate, and then obtained by using a 2D marCCD. X-ray diffraction pattern scattered from the layer. At this time, the distance from the layer to the detector is selected such that the self-assembly pattern in the layer can be effectively observed in the range of about 2 m to 3 m. As the substrate having a hydrophilic surface, a substrate having a wetting angle of about 5 degrees at room temperature for pure water is used, and as a substrate having a hydrophobic surface, a wetting angle for pure water at room temperature is about 60 degree substrate. 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 at room temperature for pure water 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 at room temperature for pure water according to the above method. It can be confirmed from the figure that there is an in-phase phase diffraction pattern in any case, and the block copolymer of Example 1 has an upright alignment property.

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

The volume fraction is as follows.

The volume fraction of each block of the block copolymer was calculated based on the molecular weight measured by GPC (gel permeation chromatography) and the density at room temperature. Among them, the density is measured by the buoyancy method, in other words, by the mass of the solvent (ethanol) (the mass and the density in the air are known), and the GPC is carried out according to the aforementioned method. The results of the GISAXS analysis of each sample are shown in Figures 18 to 20. 18 to 20 are the results of the samples 1 to 3, respectively, and it can be confirmed from the figure that the in-phase phase diffraction pattern was observed in the GISAXS, and thus it was predicted to have the upright alignment property.

Test Example 3

From Test Example 1, it was confirmed that the block copolymer in the examples had substantially excellent self-assembly. In the examples, the surface energies and densities of Comparative Examples 1 and 2 and Examples 1 to 5 (the appropriate results were observed from the others) were evaluated.

The surface energy was measured by using a droplet shape analyzer (DSA 100, product of KRUSS, Co.). The surface energy is evaluated by a polymer layer which is spin-coated on a tantalum wafer by coating a coating liquid (a material to be evaluated is dissolved in fluorobenzene so that a solid content is 2% by weight). The coating was allowed to have a thickness of 50 nm (coating area: width = 2 cm, length = 2 cm) and then allowed to dry at room temperature for about 1 hour and subjected to thermal annealing treatment at about 160 ° C for about 1 hour. form. The surface energy can be calculated from the average value, which is calculated from the average value measured by deionized water (H ₂ O) and diiodomethane (the surface tension of the two liquids are known). . In the table below, the surface energy of each block is the surface energy measured by the homopolymer formed by the monomers forming the corresponding blocks according to the above method.

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

The measured values are shown in the table below.

From the above table, it was confirmed that there was a specific tendency in the case where the appropriate self-assembly property was 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 in the range of 2.5 mN/m to 7 mN/m; however, the comparative example The absolute value of the difference between the surface energies is not in the above range. Further, the surface energy of the first block is higher than the second block and is in the range of 20 mN/m to 35 mN/m. Further, the absolute value of the difference between the densities of the first and second blocks of the block copolymers of Examples 7 to 11 was 0.3 g/cm ³ or more.

Test Example 4

The results of XRD analysis of Comparative Examples 1 and 2 and Examples 1 to 5 in which appropriate results have been observed are shown in Table 4 below.

The XRD pattern was evaluated by measuring the scattering intensity according to the scattering vector (q) by passing X-rays through the sample in the 3C beam line of Pohang Light Source. The powder obtained from the block copolymer which was not treated before any specific purification to remove impurities was used as a sample after being placed in a bath for XRD measurement. During the XRD pattern analysis, the X-rays used were X-rays having an upright size of 0.023 mm and a horizontal dimension of 0.3 mm, and the detector used was an assay device (for example, 2D marCCD). Obtaining a 2D diffraction pattern from the sample scattering, which is an image, by using silver behenate, the resulting diffraction pattern is corrected to a scattering vector (q), and then the scattering intensity is plotted according to the scattering vector (q) . The position of the peak and the FWHM are obtained by plotting the scattering intensity from the scattering vector (q) and the peak fit. From the above results, it was confirmed that the block copolymer exhibiting excellent self-assembly exhibited a specific XRD pattern as compared with the comparative example in which self-assembly was not confirmed. Specific words, the scattering vector q in the range of 0.5nm ^-1 to 10nm ^-1 observed FWHM 0.2nm ^-1 to a peak in the range of 1.5nm ^-1; however, not observed in Comparative Example such peaks .

Claims (21)

A block copolymer comprising a block represented by formula 4 as shown and when the X-ray diffraction analysis, the value of q within the range of 0.5nm ^-1 to 10nm ^-1, showing the FWHM 0.2nm ^- Peaks in the range of ¹ to 1.5 nm ^-1 : Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, having 2 An alkenyl group up to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is an oxygen atom a sulfur atom, -S(=O) ₂ -, an alkylene group having 1 to 20 carbon atoms, an extended alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and Y is a monovalent substituent comprising a chain-linked cyclic structure having 10 or more chain-forming atoms, wherein the cyclic structure is an aromatic structure having 6 to 18 carbon atoms and wherein the chain-forming atomic carbon , oxygen, sulfur or nitrogen. The block copolymer of claim 1, wherein the X-ray oxygen atom, -C(=O)-O- or -O-C(=O)-. The block copolymer of claim 1, wherein the X-form is -C(=O)-O-. The block copolymer of claim 1 wherein the chain comprises from 10 to 20 chain-forming atoms. The block copolymer of claim 1, wherein the chain-forming atom is carbon or oxygen. The block copolymer of claim 1, wherein the chain is a linear hydrocarbon chain. The block copolymer of claim 1, wherein the chain of Y is directly attached to the ring structure or is attached to the ring structure via a linker. The block copolymer of claim 7, wherein the linker is an oxygen atom, a sulfur atom, -NR ₃ -, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an alkynyl group, wherein R ₃ It is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl. The block copolymer of claim 1, wherein Y is represented by the following formula 2: [Formula 2]-PQZ wherein P is an exoaryl group, Q is a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ is Hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and Z is a chain having 10 or more chain-forming atoms. A block copolymer comprising a block represented by the formula 5, and when the X-ray diffraction analysis, the value of q within the range of 0.5nm ^-1 to 10nm ^-1, showing the FWHM 0.2nm ^- Peaks in the range of ¹ to 1.5 nm ^-1 : Wherein R is hydrogen 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, Q is an oxygen atom, and Z is A chain having 10 or more chain-forming atoms, wherein the chain-forming atom is carbon, oxygen, sulfur or nitrogen. A block copolymer according to claim 1 or 10, wherein a layer is formed which exhibits a grazing angle incident small angle X-ray scattering around a surface having a wetting angle for purified water in the range of 5 to 20 degrees. The peak of the pattern is perpendicular to the X coordinate. A block copolymer according to claim 1 or 10, wherein a layer is formed which exhibits a grazing angle incident small angle X-ray scattering around a surface having a wetting angle for purified water in the range of 50 to 70 degrees. The peak of the pattern is perpendicular to the X coordinate. The block copolymer of claim 1 or 10, wherein the number of chain-forming atoms in the chain conforms to Equation 1: [Equation 1] 3 nm ^-1 ~ 5 nm ^-1 = nq / (2 × π) wherein n is a chain atom Number, q is the smallest scattering vector in the scattering vector observed at the peak in the X-ray diffraction analysis or the scattering vector at the peak with the largest area observed in the X-ray diffraction analysis, and wherein the π is the circumference The ratio of its diameter. The block copolymer of claim 1 or 10, wherein the block of the formula 4 or 5 has a volume fraction in the range of 0.4 to 0.8. The block copolymer of claim 1 or 10, wherein further comprising a second block, and wherein the block of formula 4 or 5 and the second block The absolute value of the difference between the surface energies is in the range of 2.5 mN/m to 7 mN/m. The block copolymer of claim 1 or 10, wherein the block of the formula 4 or 5 has a surface energy in the range of from 20 mN/m to 35 mN/m. The block copolymer of claim 1 or 10, wherein further comprising a second block, and wherein the absolute value of the difference between the density of the block of the formula 4 or 5 and the second block is 0.3 g/cm ³ or higher. A polymer layer comprising the self-assembled product of the block copolymer of claim 1 or 10. The polymer layer of claim 18, which exhibits a grazing angle incident peak in a small angle X-ray scattering diffraction pattern that is perpendicular to the X coordinate. A method for forming a polymer layer comprising forming a polymer layer comprising a self-assembled product of the block copolymer of claim 1 or 10. A method of forming a pattern comprising selectively removing 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 or 10 A block other than the block represented by Formula 4 or 5 or the block represented by Formula 4 or 5 in the block copolymer.