TWI598368B - 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.

Technical purpose

This application provides block copolymers and their use.

As used herein, the term "alkyl" unless otherwise specified By analogy, it may mean an alkyl group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 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.

As used herein, the term "alkoxy" unless otherwise specified By definition, it may mean an alkoxy group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 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.

As used herein, the term "alkenyl or alkynyl" unless By definition, it 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. 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, the term "alkylene" unless otherwise By definition, it may mean 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.

As used herein, the term "alkenyl or alkynyl", Unless otherwise defined, it 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. 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 aryl group" may be a compound comprising or including 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.

As used herein, the term "aromatic structure" may refer to the aryl A aryl group or an aryl group.

As used herein, the term "alicyclic structure" unless otherwise By definition, it can 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 mean that there is no atom at the corresponding position. Happening. 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".

Optionally substituted alkyl, alkenyl, alkynyl, alkylene, The substituent of 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, a halogen atom, a carboxyl group, a glycidyl group, an acryl group or a methacrylium group. A group, an acryloxy group, a methacryloxy group, a thio group, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, but is not limited thereto.

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

The monomer used to form the block copolymer is as shown in the following formula 1:

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, because of the presence of the chain The block copolymer exhibits excellent self-assembly properties.

In one embodiment, the chain can be a linear hydrocarbon chain, such as straight Alkenyl 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. Chain can be connected to the 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 of the following formula 2 indicates.

[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 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 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 include borrowing in the presence of a free radical initiator and a living radical polymerization agent. The radical polymerization reaction polymerizes a material containing a monomer capable of forming a block.

In the manufacture of the block copolymer, it is not particularly limited for use in the form A method of forming other blocks included in the block copolymer and a block formed by the above monomers, which can be formed by selecting a suitable monomer by considering the type of the block to be formed.

The method of making a block copolymer may further include The polymerization product obtained by the method was precipitated 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 relates to a block copolymer comprising a block formed by using 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.

[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, or a carbonyl group. Base, -C(=O)-O- or -O-C(=O)-.

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

In another embodiment, the first block can be borrowed from 4 to 6 A block according to at least one of the above, wherein the at least one chain-forming atom having 8 or more chain-forming atoms has an electronegativity of 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.

Not specifically limited to the first block (such as 1A, 1B or 1C embedded The segment) is a type of another block (hereinafter may be referred to as a second block) included in the block copolymer.

For example, the second block can be a polyvinylpyrrolidone block, a poly Lactic acid block, polyvinylpyridine block, polystyrene block (such as polystyrene block or polytrimethyldecyl styrene), polyalkylene oxide block (such as polyethylene oxide embedded) Segment) 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, with the first block (eg, 1A, 1B) The second block, which is included in the block copolymer together with the 1C block, may be 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 Known as the 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 as shown in Formula 10. Block. 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 have 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. Alkyl.

In still another embodiment, the second block can include at least A block of a 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 矽原 The sub, iron atom or boron atom is not particularly limited as long as it exhibits an appropriate etching selectivity due to the difference from the other atom in the block copolymer.

The 2D block can include 1 or more, 2 or more, 3 or more Many, 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 may be an aromatic structure having 6 to 12 carbon atoms, for example, an aryl group or an aryl group.

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

[Formula 12]

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.

[Formula 13]

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 carborane Carboranyl group or silsesquioxanyl group (such as polyhedral oligomeric sesquioxanes), ferrocene or trialkyl decyloxy. However, there is no particular limitation as long as it is selected to include at least one gold The etch selectivity can be obtained by a genus or a metal atom.

In still another embodiment, the second block may include a negative electricity A block of an atom of 3 or higher 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 can be, but is not limited to, nitrogen Atom or oxygen atom.

Except for non-halogen atoms having an anion of 3 or higher, The 2E 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. 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.

[Equation 15]

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

The aryl group may include at least one or 1 to 3 inclusions having 3 Or a higher substituent of an anion-free non-halogen atom. 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.

[Formula 16]

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 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 decylamine A ethoxy group, a nitrile group, a pyridyl group or an amine group.

In another embodiment, the second block may comprise a heterocyclic ring The aromatic structure of the 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 X1 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 or Heterocyclic substituents. 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, self-contained An amine-derived substituent, 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 include at least one of the above a block 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.

The block copolymer may have, for example, about 3,000 to The number average molecular weight (Mn) in the range of 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, then Ratio of the first block in the block copolymer (for example, the block containing the chain) It can range from 10 mol% to 90 mol%.

This application relates to polymers comprising block copolymers Floor. This polymer layer can be used in a variety of applications. For example, it can be used for a 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 Periodic structures can be formed by self-assembly, including balls, cylinders, spirals, tetrahedrons, or layers.

For example, in a block copolymer, one segment can be shaped a regular structure formed in a laminated form, a cylindrical form, or the like, formed by other blocks joined to the first block or the second block via the first block, the second block, or other via a covalent bond In the segment.

The polymer layer can exhibit the above-described in-phase phase diffraction pattern, that is, The peak of the X coordinate in the GISAXS diffraction pattern perpendicular to 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 also relates to the formation of polymerization using block copolymers. The method of the layer. 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 layer of a block copolymer or a coating liquid (wherein the block copolymer is diluted in a suitable solvent) by coating or the like, and aging or heat-treating the layer as needed.

Aging or heat treatment can be based, for example, on the phase transition of the block copolymer Varying temperature or glass transition temperature, for example, higher than glass transition temperature The temperature of the degree or phase transition temperature is carried out. 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 in a non-polar solvent and/or a polar solvent The room temperature is aged for about 1 minute to 72 hours.

This application is also directed to a method of forming a pattern. this method A first or second block in the block copolymer is selectively removed 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 high aspect ratio can be formed The nanometer size pattern of yttrium oxide. For example, by forming a polymer layer on ruthenium oxide, the block copolymer in the polymer layer is selectively removed in a predetermined structure, and any block of the block copolymer is removed, and in various methods ( For example, reactive ion etching) etches yttrium oxide to form various types of patterns (such as nanorods or nanopore patterns). In addition, according to the above In the method, a nano pattern having a high aspect ratio can be formed.

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

For example, by the above method, it can be formed at about 6 to 80 nm. The pitch is set to have a pattern of nanostructures (e.g., nanowires) having a width of about 3 to 40 nm. 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.

In addition, in this structure, a naphthalene having a high aspect ratio can be formed. Rice noodles or nanopores.

In this method, the block is selectively removed without particular limitation For the method of any of the blocks, for example, a method of irradiating a suitable electromagnetic wave (for example, ultraviolet rays) to the polymer layer to remove the relatively soft block can be used. 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.

In addition, after UV irradiation, the polymer layer is acid-treated. To further remove the segment that is destroyed 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.

Figure 1 shows an SEM image of a polymer layer.

Figure 2 shows the etch selectivity.

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.

1. 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). In a 5 mL vial, an example or comparative example of the embedded assay to be determined The segment copolymer or macroinitiator is diluted to a concentration of about 1 mg/mL. 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. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as a mobile phase, and the obtained product was recrystallized from a mixed solvent of methanol and water (mixed in a 1:1 weight ratio), thereby obtaining a white solid. Product (DPM-C12) (7.7 g, 22.2 mmole), yield 63%.

<NMR 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.

Example 1

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) reagent (2-cyano-2-propyldodecyltrithiocarbonate) 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 is dissolved (concentration: 30% by weight), after The 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.

Comparative 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 split 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.

Test example 1

A self-assembled polymer layer was obtained by using the block copolymer of Example 1 and the results were observed. In other words, the 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 was performed by thermal annealing at 160 ° C for 1 hour. Thereafter, the polymer layer was subjected to SEM (Scanning Electron Microscope) analysis to evaluate self-assembly. Figure 1 shows the results of Example 1, and from the above, it can be confirmed that proper phase separation is achieved.

Test example 2

The etching resistance was evaluated for the block copolymer of Example 1 or Comparative Example 1. Specifically, an etching process was performed under the same conditions (RF power: 150 W, pressure: 15 mTorr) by an etching apparatus (SNTech), and etching selectivity was compared. The results are shown in Figure 2. In Figure 2, the X-axis is the etch time, which is the percentage of film thickness remaining during the etch process. In FIG. 2, PDPM exhibits etching time for the first block of Example 1 and Comparative Example 1, while PTFSis exhibits etching time for the second block of Example 1, and PPFS exhibits etching time for the second of Comparative Example 1. Block. From Fig. 2, it was confirmed that the block copolymer of Example 1 exhibited excellent etching selectivity because of a large difference between the first block etching resistance and the second block etching resistance.

Claims (10)

A block copolymer comprising a first block represented by the following formula 5 and a second block represented by the following formula 11 and comprising at least one metal atom or metalloid atom: Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, -C(=O)-O- or -OC(=O)-, and P is a stretch having 6 to 30 carbon atoms. Aryl, Q is an oxygen atom or -NR ₃ -, wherein R ₃ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkyne having 2 to 20 carbon atoms a group having an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and Z is a linear chain having 8 or more chain-forming atoms, wherein the chain-forming atomic group is carbon or oxygen , sulfur or nitrogen and the number of chain-forming atoms is from 8 to 20; Wherein B is a monovalent substituent having an aromatic structure, and the aromatic structure has 6 to 12 carbon atoms and contains a halogen atom and a substituent containing a metal atom or a metalloid atom. The block copolymer of claim 1, wherein the chain-forming atom is carbon or oxygen. The block copolymer of claim 1, wherein the linear hydrocarbon chain. The block copolymer of claim 1, wherein the metal atom or metalloid atom is ruthenium, iron or boron. The block copolymer of claim 1, wherein the halogen atom is fluorine. The block copolymer of claim 1, wherein the second block is represented by the following formula 13: Wherein X ₂ is a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms An alkynyl group having 2 to 20 carbon atoms, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein R ₁ is hydrogen, an alkane having 1 to 20 carbon atoms a group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, X ₁ is a single bond, 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 having 2 to 20 carbon atoms An alkynyl group, each of R ₁ to R ₅ is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, a halogen atom or a substitution including a metal or a metalloid atom A group, wherein at least one of R ₁ to R ₅ contains a halogen atom, and at least one of R ₁ to R ₅ is a substituent including a metal or a metalloid atom. The block copolymer of claim 1, wherein the metal atom or metalloid atom is contained in a carboranyl group or a sesquiphenylene oxide group, a ferrocenyl group or a trialkyl decyloxy group. A polymer layer comprising the self-assembled product of the block copolymer of claim 1. A method for forming a polymer layer comprising forming a polymer layer comprising a self-assembled product of the block copolymer of claim 1. A method of forming a pattern comprising selectively removing a laminate 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 in the segment copolymer.