TWI586691B - Block copolymer - Google Patents

Description

Block copolymer

This invention relates to block copolymers.

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

Description Technical purpose

The present invention provides block copolymers and uses thereof.

Solution

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

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

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

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

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

The term aryl or aryl hydrazine as used herein may be A monovalent or divalent structure derived from a compound comprising a benzene ring structure or a structure in which at least two benzene rings are bonded by one or two carbon atoms or bonded by a random linking group, or a derivative of the compound, unless otherwise Other definitions. The aryl or extended aryl group may be an aryl group having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms unless otherwise defined.

The term "fluorene-aromatic structure" as used herein may refer to an aryl group. Or stretch the base.

The term rouge ring structure as used herein may mean no It is a cyclic hydrocarbon structure of an aromatic cyclic structure. The lipid ring structure may be a structure having 3 to 30, 3 to 25, 3 to 21, 3 to 18, or 3 to 13 carbon atoms unless otherwise defined.

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

Optionally substituted alkyl, alkenyl, alkynyl, alkylene, The substituents of an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryl group, a chain, an aromatic structure and the like may be a hydroxyl group, a halogen atom, a carboxyl group, a glycidyl group, an acrylonitrile group, a methacryl group. Anthracenyl, acryloxy, methacryloxy, thiol, alkyl, alkenyl, alkynyl, alkyl, alkenyl, alkynyl, alkoxy or aryl, but not limited to this.

In one embodiment, it may be provided as expressed in Equation 1 below. A monomer having a novel structure and capable of forming a block copolymer.

In Formula 1, R hydrogen or alkyl, and X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenyl group, an alkynyl group, -C(= O)-X ₁ - or -X ₁ -C(=O)-. In the above formulas, X ₁ may be an oxygen atom, a sulfur _{atom, -S (= O) 2 -} , alkylene, alkenylene group or alkynyl group extension, and Y 8 may comprise one or more chains having formed A monovalent substituent of a cyclic structure linked by a chain of atoms.

In another embodiment, in Equation 1, X can be a single A bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -O-C(=O)-; or X may be -C(=O)-O-, but is not limited thereto.

In Formula 1, the monovalent substituent Y includes at least 8 shapes A chain structure formed by chains of atoms.

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

Block copolymerization when the compound of formula 1 forms a block copolymer The object 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 Linear alkyl. In this example, the alkyl group may be an alkyl group having 8 or more, 8 to 30, 8 to 25, 8 to 20, or 8 to 16 carbon atoms. At least one carbon atom in the alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom in the alkyl group may be optionally substituted with another substituent.

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

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

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

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

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

In Formula 2, Q may be appropriate an oxygen atom or -NR ₁ -, in which R ₁ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group.

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

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

In Formula 3, R is a hydrogen atom or has 1 to 4 carbon atoms. An alkyl group, 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 an atom having 8 or more chain-forming atoms. The above chain.

Another embodiment of the invention relates to a method for preparing embedded A method of a segment copolymer comprising the step of forming a block by polymerizing a monomer.

The specific method used to prepare the block copolymer is not particularly The limitation is as long as it comprises the step of forming at least one block of the block copolymer by using the above monomers.

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

In one embodiment, the block copolymer can be used by Method Preparation: Polymerization of a material comprising a monomer capable of forming a block in the presence of a free radical initiator and a living radical polymerization reagent is carried out by living radical polymerization.

In the preparation of the block copolymer, used to form and The method in which the blocks formed by the monomers together include other blocks in the block copolymer is not particularly limited, and other monomers may be formed by selecting an appropriate monomer in consideration of the kind of the block to be formed. .

The method for preparing a block copolymer may additionally include The polymerization product produced by the above method is precipitated in a solvent.

The type of free radical initiator can be considered in consideration of polymerization efficiency With appropriate selection, there is no particular limitation, and an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-(2,4-dimethylvaleronitrile), or A peroxide compound such as benzhydryl peroxide (BPO) or di-tertiary butyl peroxide (DTBP).

LRP can be carried out in a solvent such as dichloromethane, 1,2-di Ethyl chloride, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide, two Methyl hydrazine or dimethyl acetamide.

For example, an alcohol such as methanol, ethanol, n-propanol or Isopropanol), a diol such as ethylene glycol or an ether compound such as n-hexane, cyclohexane, n-heptane or petroleum ether is used as the non-solvent, but is not limited.

Yet another embodiment of the present invention relates to the use of a monomer A block copolymer of the formed block (hereinafter may be referred to as a first block).

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

In Formula 4, R, X, and Y can be respectively related to Formula 1. The same as described for R, X and Y.

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

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

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

In another embodiment, the first block can be a table of formula 6 Show the block. Such a first block may be referred to herein as a 1B block.

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

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

The above description regarding Equation 1 can be applied in the same way as A particular embodiment of the chain Y in the 1B block.

In another embodiment, the first block can be in the formula 4 to 6 At least one of the blocks denotes a block in which at least one of the chains forming the chain of 8 or more chain-forming atoms has an electronegativity of 3 or more. In another embodiment, the electrons forming the atoms of the chain may have an electronegativity of 3.7 or less. Such a block may be referred to herein as a 1C block. A nitrogen atom or an oxygen atom may be exemplified as an atom having an electronegativity of 3 or more, but is not limited thereto.

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

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

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

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

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

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

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

Furthermore, the halogen atoms included in Formula 7 may be but not It is limited to a fluorine atom or a chlorine atom, and is preferably a fluorine atom.

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

For example, the block represented by Formula 7 (which is a 2B block) may It is represented by the following formula 8.

In Formula 8, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an alkynyl group, and W may be An aryl group substituted with at least one halogen atom. In the above formula, W may be an aryl group substituted with at least one halogen atom, for example, having 6 to 12 carbon atoms and having 2 or more, 3 or more, 4 or more, or 5 or more halogens An atom-substituted aryl group.

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

In Formula 9, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and R ₁ to R ₅ may each independently be a hydrogen, an alkyl group, a haloalkyl group or a halogen atom. The number of halogen atoms included in R ₁ to R ₅ is 1 or more.

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

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

In one embodiment, the second block can be in the form of Formula 10. Show the block. Such a block as used herein may be referred to as a 2C block.

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

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

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

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

The metal atom or metalloid atom in the 2D block may be ruthenium An atom, an iron atom or a boron atom, but is not particularly limited as long as it A suitable etch selectivity can be exhibited due to the difference from another atom in the block copolymer. 2D blocks can include 1 or more, 2 or more, 3 or more

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

The 2D block can be represented by Formula 11.

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

The aromatic structure of Formula 11 may have 6 to 12 carbon atoms An aromatic structure such as an aryl group or an aryl group.

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

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

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

The aryl group may include at least one or one to three including a metal former Substituents of a sub- or metal-like atom and 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms.

Which may include 10 or less, 9 or less, 8 or more Less, 7 or less, or 6 or fewer 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 -, alkylene, alkenylene group or an alkynyl group extension, R ₁ to R ₅ may be each independently hydrogen, alkyl, haloalkyl, or a halogen atom A substituent including a metal or metalloid atom is presupposed that at least one of R ₁ to R ₅ includes a halogen atom, and at least one of R ₁ to R ₅ is a substituent including a metal or a metalloid atom.

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

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

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

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

The non-halogen atom in the 2E block can be, but is not limited to, a nitrogen source Sub or oxygen atom.

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

The 2E block can be represented by Formula 14.

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

The aromatic structure of Formula 14 may have 6 to 12 carbon atoms An aromatic structure such as an aryl group or an aryl group.

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

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

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

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

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

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, a sulfur _{atom, -NR 2 -, - S (} = O) 2 -, alkylene, alkenylene group or alkynyl group extension, and R ₁ to R ₅ may be each independently hydrogen, alkyl, haloalkyl, a halogen atom And a substituent including a non-halogen atom having an electronegativity of 3 or more. In the above formula, R ₁ to R ₅ is at least one of a halogen atom, and R ₁ to R ₅ is at least one of which is 3 include a halogen atom, or a non-negative power of the larger substituents.

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

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

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

In another embodiment, the second block can include impurities The aromatic structure of the ring substituent. Such a second block may be referred to herein as a 2F block.

The 2F block can be represented by Formula 17.

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

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

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, A sulfur atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and W may be an aryl group having 6 to 12 carbon atoms and having a heterocyclic substituent.

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

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

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

The above heterocyclic substituent may be, but not limited to, self-imide Derivatized substituents, substituents derived from thiopene, substituents derived from thiazole, substituents derived from carbazole or substituents derived from imidazole.

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

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

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

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

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

As used herein, the term "vertical" is considered to account for errors. The term, and for example, may include errors within ±10 degrees, ±8 degrees, ±6 degrees, ±4 degrees, or ±2 degrees.

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

In this document, depending on the nature of the temperature change (such as Wet angles are measured at room temperature unless otherwise defined. The term "room temperature" as used herein may refer to the temperature of its natural state that is not heated and cooled, and may refer to a temperature ranging from about 10 ° C to 30 ° C, or about 25 ° C or about 23 ° C.

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

The above-mentioned peak block copolymer can be displayed in GISAXS It exhibits excellent self-assembly properties and can effectively control this property according to the target.

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

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

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

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

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

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

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

As described below, at least one of the block copolymers therein In the case where the block includes a chain, the number of atoms forming the chain (n) and the scattering vector (q) obtained from the XRD analysis can satisfy the following Equation 1.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

If the block copolymer includes at least the first and second blocks, then The ratio of the first block (e.g., the block comprising the chain) in the block copolymer can range from 10 mole% to 90 mole%.

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

In one embodiment, the blocks in the polymer layer are The polymer can form a periodic structure by self-assembly, including a sphere, a cylinder, a pentagonal tetrahedron or a sheet.

For example, the first block or the second inlay in the block copolymer The segments may be joined to one segment of the other blocks of the above blocks via covalent bonds, and the other segments may form a regular structure, such as a sheet form, a cylindrical form, and the like.

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

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

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

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

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

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

For example, the pattern can be formed on the order of tens of nanometers, and this The pattern can be used in a variety of applications, including next-generation information electronic magnetic recording media.

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

In addition, this structure can be formed to have a high aspect ratio Rice noodles or nanopores.

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

In addition, after irradiation with ultraviolet rays, the polymer layer can be It is treated with an acid to further remove the segment degraded by ultraviolet rays.

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

effect

Figures 1 to 4 are SEM images of polymer layers.

The present invention can provide block copolymers and applications thereof. Block copolymers have excellent self-assembly properties and phase separation, as well as a variety of functions necessary for the application.

Exemplary implementation

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

NMR analysis

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

<abbreviation>

Br=wide peak signal, s=single peak, d=double peak, dd=double double peak, t=triplet, dt=double triplet, q=quadruple, p=fivet, m=multiple peak

2. GPC (gel permeation chromatography)

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

<GPC measurement conditions>

Device: 1200 Series from Agilent technologies, Co.

Column: Using two Polymer laboratories, Co. PLgel mixed B

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg/ml, 200 μL injection

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

Preparation Example 1

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

<NMR analysis results of intermediates>

^{1 H-NMR (DMSO-d} ): δ6.69 (dd, 2H); δ6.53 (dd, 2H); δ3.05 (t, 2H); δ1.59 (p, 2H); δ1.40- 1.26(m,16H); δ0.88(t,3H) The intermediate to be synthesized (1.98 g, 7.1 mmol), methacrylic acid (0.92 g, 10.7 mmol), dicyclohexylcarbazide Amine (DCC; 2.21 g, 10.7 mmol) and p-dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmol) were placed in a flask, 100 mL dichloromethane was added and at room temperature The reaction was carried out for 24 hours under nitrogen. After the reaction was completed, the urea salt produced during the reaction was removed via a filter and the remaining dichloromethane was also removed. The impurities were removed via column chromatography using hexane and DCM (dichloromethane) as the mobile phase, and the obtained product was in a mixed solvent of methanol and water (methanol: water = 3:1 (weight ratio)) Crystallization, whereby a white solid product (DPM-N2) (1.94 g, 5.6 mmol) having a yield of 79% was obtained.

<Results of NMR analysis on DPM-N2>

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

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

Preparation Example 2

The compound of the following formula G (DPM-C4) was synthesized by the following method. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromobutane (23.5 g, 94.2 mmol) were added to a 250 mL flask and dissolved in 100 mL acetonitrile, and excess potassium carbonate was added thereto and then The mixture was reacted at 75 ° C under nitrogen for about 48 hours. After the reaction, the remaining potassium carbonate and acetonitrile used for the reaction were removed. Dichloromethane (DCM) with a mixed solvent of water organize, and the organic layer was collected and separated by the dewatering MgSO _4. A white solid intermediate having a yield of about 37% was then obtained via column chromatography using DCM.

The intermediate to be synthesized (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmol) and Dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) was placed in a flask, 120 ml of dichloromethane was added, and the reaction was carried out under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt produced in the reaction was removed via a filter, and the remaining dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as the mobile phase, and the obtained product was recrystallized in a mixed solvent of methanol and water (mixed in a weight ratio of 1:1), This gave the product as a white solid (DPM-C4).

<Results of NMR analysis on DPM-C4>

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

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

Example 1

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

Comparative example 1

2.0 g of the compound of Preparation Example 2 (DPM-C4), 64 mg of RAFT (reversible addition fragmentation chain transfer) reagent (cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile) ) and 5.34 Million benzene was placed in a 10 ml flask (Schlenk flask), and then the mixture was stirred at room temperature under nitrogen for 30 minutes, and then subjected to RAFT (reversible addition fragmentation chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, and then subjected to vacuum filtration and drying to obtain a pink macroinitiator.

3.0 g of the giant initiator, 2.7174 g of pentafluorostyrene and 1.306 ml of benzene were placed in a 10 ml flask (Schlenk flask), and then the mixture was stirred at room temperature under nitrogen for 30 minutes, and then at 115 ° C. 4 hours of RAFT (reversible addition fragmentation chain transfer) polymerization. After the polymerization, the solution of the reaction was precipitated in 250 ml of methanol as an extraction solvent, and then subjected to vacuum filtration and dried to obtain a pale pink block copolymer. The block copolymer includes a first block derived from the compound of Preparation Example 2 (DPM-C4) and a second block derived from pentafluorostyrene.

Comparative example 2

The block copolymer was prepared in the same manner as in Comparative Example 1, except that a macroinitiator and pentafluorobenzene prepared by using 4-methoxyphenyl methacrylate instead of the compound of Preparation Example 2 (DPM-C4) were used. Other than ethylene. The block copolymer comprises a first block derived from 4-methoxyphenyl methacrylate and a second block derived from pentafluorostyrene.

Comparative example 3

The block copolymer was prepared in the same manner as in Comparative Example 1, except that a macroinitiator prepared by using the dodecyl methacrylate instead of the compound of Preparation Example 2 (DPM-C4) and pentafluorostyrene were used. The block copolymer comprises a first block derived from dodecyl methacrylate and a second block derived from pentafluorostyrene.

Test example 1

Self-assembled polymer layer by using Example 1 and ratio The block copolymers of Examples 1 to 3 were prepared and observed. Specifically, each block copolymer was dissolved in a solvent to a concentration of 1.0% by weight and then spin-coated on a tantalum wafer at a speed of 3000 rpm for 60 seconds. Self-assembly is then carried out by solvent annealing or thermal annealing. The solvents and aging methods used are set forth in Table 1 below. Each polymer layer was then subjected to SEM (Scanning Electron Microscopy) or AFM (Atomic Force Microscopy) analysis to evaluate self-assembly properties. 1 is the result of Example 1, and FIGS. 2 to 4 are the results of Comparative Examples 1 to 3, respectively.

Claims (14)

A block copolymer comprising a block represented by the following formula 6 and a second block represented by the following formula 8: Wherein R ¹ and R ² are each independently 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, an alkenyl group, and a stretching group. Alkynyl, -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 -, a carbonyl group, An alkyl group, an alkenyl group or an alkynylene group, T is an extended aryl group having 6 to 13 carbon atoms, Q is a single bond, and Y is a chain having 9 to 16 chain-forming atoms, wherein the chain is linear Hydrocarbon chain, Wherein X ₂ is a single bond or alkylene group having 1 to 4 carbon atoms, and W is a halogen atom comprising at least one of an aryl group having 6 to 13 carbon atoms. A block copolymer according to the first aspect of the invention, wherein X is an oxygen atom, a carbonyl group, -C(=O)-O- or -O-C(=O)-. The block copolymer according to claim 1, wherein the second block is represented by the following formula 9: Wherein X ₂ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ₁ to R ₅ are each independently hydrogen, alkyl or haloalkyl or a halogen atom; and are included in R ₁ to R ₅ The number of halogen atoms is 1 or more. The block copolymer according to claim 3, wherein the number of halogen atoms included in R ₁ to R ₅ is 3 or more. The block copolymer according to item 3 of the patent application, wherein the number of halogen atoms included in R ₁ to R ₅ is 5 or more. The block copolymer according to claim 1, wherein the halogen atom is fluorine. According to the patent application range block copolymer, Paragraph 1, wherein when an X-ray diffraction, it exhibits from 0.5 nm to 10 nm ^-1 Q ^-1 of the value range of the FWHM (full width at half maximum) in the range of 0.2 nm ^-1 to a peak of 1.5 nm ^-1. The block copolymer according to claim 1 wherein the block fraction represented by Formula 6 is in the range of from 0.4 to 0.8, and the volume fraction of the second block is from 0.2. To the extent of 0.6. The block copolymer according to claim 1, wherein the absolute value of the difference between the surface energy of the block and the second block represented by Formula 6 is from 2.5 millinewtons per meter to 7 millinewtons. Within the range of / meter. The block copolymer according to the first aspect of the patent application, wherein the surface energy of the block represented by Formula 6 is in the range of from 20 mN/m to 35 mN/m. The block copolymer according to claim 1, wherein the difference between the density of the block and the second block represented by Formula 6 is 0.3 g/cm 3 or more. A polymer layer comprising the self-assembled product of the block copolymer of claim 1 of the patent. A method for forming a polymer layer comprising forming a polymer layer comprising a self-assembled product of the block copolymer of claim 1 of the patent application. A pattern forming method comprising selectively removing a block copolymer from a laminate comprising a substrate and a polymer layer formed on the substrate and comprising a self-assembled product of the block copolymer of claim 1 The first block or the second block of matter.