KR102484627B1 - Pinning layer composition - Google Patents

Abstract

This application is directed to pinning layer compositions. The present application can effectively secure the desired degree of crosslinking even through a low-temperature process, can form a uniform thin film with excellent coating properties, has high adhesion to the substrate, and has low reactivity to the neutral brush layer. The branching can provide a pinning layer composition capable of forming a pinning layer.

Description

Pinning layer composition

This application relates to a pinning layer composition.

A block copolymer is a copolymer in which polymer blocks having different chemical structures are connected through covalent bonds. Such a block copolymer may form a periodically arranged structure such as a sphere, a cylinder, or a lamella by phase separation. The shape and size of the domains of the structure formed by the self-assembly of the block copolymer can be controlled in a wide range, for example, by the type of monomers forming each block or the relative ratio between the blocks.

Due to these characteristics, the application of block copolymers to fabrication of various next-generation nanodevices such as nanowires, quantum dots or metal dots, or lithography methods capable of forming high-density patterns on a predetermined substrate has been studied. (For example, see Non-Patent Document 1, etc.).

In order to apply the block copolymer to the above applications, a process capable of controlling the directionality and positioning of the phase separation pattern of the block copolymer is required. (chemoepitaxy) processes are known.

The pinning layer may act as a chemical preliminary pattern on the substrate. A method of forming a pinning layer on a conventional substrate is a method of forming a pinning layer composition on a substrate and crosslinking it through thermal annealing or the like. However, since the known pinning layer composition requires a high-temperature aging process in order to secure a sufficient crosslinking degree, chemical transformation of the pinning layer occurs during the crosslinking process, and thus does not exhibit the desired effect in many cases.

In addition, the pinning layer composition forming the pinning layer needs to have coating properties in order to obtain a uniform thin film, and needs to have adhesion to the substrate and low reactivity with a neutral brush layer. .

Chaikin and Register. et al., Science 276, 1401 (1997)

This application provides a pinning layer composition. The present application can effectively secure the desired degree of crosslinking even through a low-temperature process, can form a uniform thin film with excellent coating properties, has high adhesion to the substrate, and has low reactivity to the neutral brush layer. One object is to provide a pinning layer composition capable of forming a pinning layer.

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

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

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

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

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

In this specification, the term aryl group or arylene group, unless otherwise specified, has a benzene ring structure, two or more benzene rings are connected while sharing one or two carbon atoms, or connected by any linker It may mean a monovalent or divalent residue derived from a compound having a structure or a derivative thereof. Unless otherwise specified, the aryl group or arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms.

In this application, the term aromatic structure may mean the above aryl group or arylene group.

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

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

In the present application, substituents that may be optionally substituted on an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, a chain or an aromatic structure, etc. include a hydroxyl group, a halogen atom , carboxyl group, glycidyl group, acryloyl group, methacryloyl group, acryloyl group oxy, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group , An alkoxy group or an aryl group may be exemplified, but is not limited thereto.

Unless otherwise specified, among the physical properties mentioned in this application, the physical properties that can be changed by temperature are values measured at room temperature. The term room temperature is a natural temperature that is not warmed or cooled, and may mean a temperature of about 10 ° C to 30 ° C, about 25 ° C or about 23 ° C.

This application is directed to pinning layer compositions. The term pinning layer composition may refer to a composition capable of forming a pinning layer. The meaning of pinning layer is as known in the art. Unlike the neutral brush layer, which is controlled to exhibit similar affinity to both blocks of the block copolymer in order to induce homeotropic orientation of the block copolymer, the pinning layer is usually applied to either block of the block copolymer. It is designed to show excellent affinity compared to other blocks.

The pinning layer composition of the present application may include at least a random copolymer. The pinning layer composition may include the random copolymer as a main component. That is, based on the total weight of the pinning layer composition, the random copolymer is included in an amount of about 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. can The upper limit of the ratio of the random copolymer is approximately 100% by weight. In addition, when the pinning layer composition includes a solvent, the ratio may be a ratio measured with respect to the weight excluding the solvent.

The random copolymer may include a unit of Formula 1 below or a unit of Formula 2 below.

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z may be a hydrocarbon chain having 8 to 20 carbon atoms.

[Formula 2]

In Formula 2, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms.

In Formula 1, X may be an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, or -C(=O)-O- in another example, but is not limited thereto no.

In Formula 1, P may be an arylene group having 6 to 18 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a phenylene group.

In Formula 1, Q may be connected to the para position when P is a phenylene group.

Q in Formula 1, in one example, may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O)- , For example, it may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, but is not limited thereto.

Z in Formula 1 is a hydrocarbon chain having 8 to 20 carbon atoms. In another example, the number of carbon atoms in the hydrocarbon chain may be 9 or more, 10 or more, 11 or more, or 12 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less. The hydrocarbon chain may be a straight chain hydrocarbon chain, and may be, for example, a straight chain alkyl group, an alkenyl group or an alkynyl group. The number of carbon atoms in the straight-chain alkyl group, alkenyl group or alkynyl group is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, or 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, It may be 13 or less or 12 or less.

In one example, the hydrocarbon chain is a chain including a straight chain structure, and at this time, the number of carbon atoms forming the straight chain structure may be within the range of 8 to 20. The chain may be straight or branched, but the number of carbon atoms calculated only by the number of carbon atoms forming the longest straight chain may be within the range of 8 to 20. In the case of a branched chain, the number of carbon atoms forming the straight chain structure can be calculated as the number of carbon atoms forming the longest chain. For example, when the chain is an n-pentyl group, the number of carbon atoms forming the linear structure is 5, and when the chain is a 2-methylpentyl group, the number of carbon atoms forming the linear structure is 5.

The hydrocarbon chain including the straight-chain structure may be a straight-chain or branched-chain alkyl, alkenyl, or alkynyl group, wherein the number of carbon atoms forming the straight-chain structure is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less.

In one example, one or more of the carbon atoms of the alkyl group, alkenyl group, or alkynyl group, which is the hydrocarbon chain, may be optionally replaced with a hetero atom for a carbon atom such as an oxygen atom, and at least one of the alkyl group, alkenyl group, or alkynyl group A hydrogen atom may be optionally substituted by another substituent.

In the unit represented by Formula 2, X ₂ may be a single bond in one example.

In Formula 2, the aryl group may be, for example, an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms, or a phenyl group.

As the halogen atom included in Formula 2, a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately exemplified, but is not limited thereto. The halogen atom may be substituted with the aryl group.

In one example, W in Formula 2 has 6 to 18 carbon atoms or 6 to 12 carbon atoms substituted with 1 or more, 2 or more, 3 or more, 4 or more or 5 or more halogen atoms (fluorine atoms or chlorine atoms, etc.) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms substituted in the above is not particularly limited, and for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms may be present.

The unit of Formula 2 may be represented by Formula 6 below in another example.

[Formula 6]

In Formula 6, X ₂ is a single bond, an oxygen atom or a sulfur atom, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms included in R ₄ to R ₈ is There may be three or more.

In Formula 6, X ₂ may be a single bond in another example.

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

The halogen atoms may be included in a haloalkyl group, and one or more, two or more, three or more, four or more, or five of R ₄ to R ₈ may be halogen atoms. In this case, the halogen atom may be a fluorine atom or a chlorine atom.

The random copolymer may include only any one of the units of Chemical Formula 1 or 2, or may include both of the above units.

The total molar ratio of units represented by Formula 1 or 2 in the random copolymer may be approximately 70 mol% or more, or 75 mol% or more, or 90 mol% or less, 85 mol% or less, or 80 mol% or less. When the random copolymer includes only any one of the units of Chemical Formula 1 or 2, the ratio of the units may be within the aforementioned range.

On the other hand, when the random copolymer includes units of Formulas 1 and 2 at the same time, the number of moles of units represented by Formula 1 relative to the total number of moles (A) of units represented by Formulas 1 and 2 in the random copolymer ( The ratio (B/A) of B) may be less than 0.1 or greater than 0.24.

When the ratio (B/A) is less than 0.1, the ratio (B/A) may be greater than 0, and when greater than 0.24, the ratio may be less than 1.

Selection of appropriate units among the units of Chemical Formulas 1 and 2, or the ratio thereof, in consideration of the characteristics of the desired pinning layer, for example, the pinning layer has an excellent affinity for any one block of the block copolymer compared to other blocks May be chosen to represent Mars.

The random copolymer, as an additional unit, a unit represented by the following formula (3); and a unit containing a crosslinkable functional group.

[Formula 3]

In Formula 3, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxyl group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylenyl having 1 to 4 carbon atoms can

In the above, the alkylene group of L may be a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms in one example.

In one example, L in the unit of Formula 3 is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group. R ₂ may be a hydroxy group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, and L ₁ may be an alkylene group having 1 to 4 carbon atoms. .

By presenting the unit of Chemical Formula 3 together with the crosslinkable functional group-containing unit in the random copolymer, the desired degree of crosslinking can be appropriately secured even at a low temperature in the process of forming the pinning layer, and uniform coating of the composition of the pinning layer can be achieved. It is possible, and a pinning layer having excellent adhesion to the substrate and exhibiting a desired level of reactivity to the neutral layer can be formed.

Units as described above may be formed by polymerizing monomers such as (meth)acrylic acid or phosphoethyl (meth)acrylate in the production process of the random copolymer.

The random copolymer may include the unit of Chemical Formula 3 in an amount of about 3 to 20 mol%. In another example, the ratio is about 5 mol% or more, 7 mol% or more, or 9 mol% or more, or less than about 20 mol%, 19 mol% or less, about 18 mol% or less, 16 mol% or less, 14 mol% or less, or 12 mol% or less may be sufficient.

Under these ratios, the action of the desired unit of formula (3) can be properly secured.

The cross-linkable functional group-containing unit may be applied to realize a cross-linked structure during formation of the pinning layer. The unit is a crosslinkable functional group, for example, a hydroxy group, a glycidyl group, an epoxy group, an isocyanate group, a glycidyl group, a functional group of the following formula A, a benzoylphenoxy group, an alkenyloxycarbonyl group, a (meth)acryloyl group And/or it can be formed by copolymerizing a monomer having an alkenyloxyalkyl group with a random copolymer.

[Formula A]

In Formula A, Y is a single bond, an alkylene group, an alkenylene group, or an alkynylene group, and L ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenylene group, or an alkynyl A rene group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group , an alkenylene group or an alkynylene group.

The functional group of Formula A is a substituent having a crosslinkable azide moiety at its terminal, and this functional group can be crosslinked.

In Formula A, Y may be an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms in another example.

In Formula A, L ₁ may be a single bond, an oxygen atom, -C(=O)-O- or -OC(=O)- in another example, but is not limited thereto.

As a monomer unit containing a crosslinkable functional group, a unit represented by Formula 4 below may be exemplified.

[Formula 4]

In Formula 4, R ₃ is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom.

In Formula 4, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. These alkyl groups may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents.

In Formula 4, T may be an alkylene group, an alkenylene group, or an alkynylene group in another example. In the above, the alkylene group may be an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. This alkylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents. In the above, the alkenylene group may be an alkenylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. This alkenylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents. In the above, the alkynylene group may be an alkynylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. This alkynylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents.

The divalent hydrocarbon group of T in Formula 4 may further contain a hetero atom, if necessary. In the above, the heteroatom is a heteroatom for carbon, and examples thereof include oxygen, nitrogen, or sulfur. 1 to 4 or less of these heteroatoms may be included in T of Formula 4.

Examples of monomers capable of forming the unit of Chemical Formula 4 are not particularly limited. For example, as a monomer capable of forming the unit of Chemical Formula 4, glycidyl (meth)acrylate and the like may be exemplified.

The ratio of the crosslinkable functional group-containing unit in the random copolymer is approximately 1 to 30 mol%. In other examples, the ratio is about 3 mol% or more, 5 mol% or more, 7 mol% or more, or 9 mol% or more, or 28 mol% or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, 20 mol% or less. % or less, 18 mol% or less, 16 mol% or less, 14 mol% or less, or 12 mol% or less, but is not limited thereto.

The random copolymer may additionally contain lactone group-containing units. Such a unit may help to form a pinning layer having excellent interfacial adhesion.

As such a unit, for example, a unit represented by the following formula (5) may be exemplified.

[Formula 5]

In Formula 5, R ₉ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₁₀ is -L ₂ -U, wherein L ₂ is a single bond, an alkylene group having 1 to 4 carbon atoms or an oxygen atom, and U is a lactone group. can

Appropriately in the above formula, L may be an oxygen atom.

In addition, the lactone group may be, in one example, a lactone group having 2 to 12 carbon atoms or 2 to 6 carbon atoms, and examples thereof include an alpha-acetolactonyl group and a beta-propiolactonyl group. group) or gamma-butyrolactonyl, etc. may be exemplified, but are not limited thereto.

When included, the ratio of the lactone group-containing unit in the random copolymer may be approximately 0.01 to 40 mol%. In other examples, the ratio is approximately 0.05 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 2 mol% or more, or 3 mol% or more, or 38 mol% or less, 36 mol% or less, 34 mol% or less. % or less, 32 mol% or less, 30 mol% or less, 28 mol% or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, 20 mol% or less, 18 mol% or less, 16 mol% or less, 14 mol% or less % or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, 6 mol% or less, or 4 mol% or less, but is not limited thereto.

The random copolymer may further include other units as long as the desired effect is secured in addition to the above units. Additional units included in the random copolymer may include functional monomers having various functional functional groups, and the functional monomers may be appropriately selected according to physical properties required for the pinning layer including the random copolymer. The functional monomer may be, for example, a unit of a monomer capable of improving adhesion in order to improve adhesion between substrates, but is not limited thereto.

The random copolymer may have a number average molecular weight (Mn) in the range of, for example, 2,000 to 500,000. In another example, the number average molecular weight may be 3,000 or more, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, 20,000 or more, 30,000 or more, or about 35,000 or more. In another example, the number average molecular weight may be about 400,000 or less, 300,000 or less, 200,000 or less, 100,000 or less, 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, or 40,000 or less. In the present specification, the term number average molecular weight is a value in terms of standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight refers to the number average molecular weight unless otherwise specified. In addition, unless otherwise specified, the unit of number average molecular weight is g/mol. The molecular weight of the random copolymer may be adjusted in consideration of the desired physical properties of the pinning layer.

A method for preparing the random copolymer as described above is not particularly limited. For example, the random copolymer may be prepared by applying a free radical polymerization method or a living radical polymerization (LRP) method. Examples of the LRP method described above include anionic polymerization and polymerization in which an organic rare earth metal complex or an organic alkali metal compound is used as an initiator and polymerization is performed in the presence of an inorganic acid salt such as an alkali metal or alkaline earth metal salt or an organoaluminum compound. Atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerizer as yesterday, and ARGET (Activators Regenerated by Electron Regenerated by Electron), which uses an atom transfer radical polymerizer as a polymerization control agent and proceeds polymerization under an organic or inorganic reducing agent that generates electrons. Transfer) atom transfer radical polymerization (ATRP), Initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization, reversible addition-cleavage chain transfer polymerization using inorganic reducing agent reversible addition-cleavage chain transfer (RAFT) or organic A method using a tellurium compound as an initiator and the like can be exemplified, and an appropriate method can be employed from among the above methods.

The kind of radical initiator that can be used in the polymerization process is not particularly limited. For example, AIBN (azobisisobutyronitrile), ABCN (1,1'-Azobis (cyclohexanecarbonitrile)) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis-(2,4 Azo-based initiators such as -dimethylvaleronitrile) or peroxide-based initiators such as BPO (benzoyl peroxide) or DTBP (di-tert-butyl peroxide) may be applied. For example, thermal self-initiation of styrene-based monomers Like the method using initiation), a polymerization method without using an initiator may also be applied depending on the type of monomer.

The polymerization process may be carried out, for example, in an appropriate solvent. In this case, applicable solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, anisole, and acetone. , Solvents such as chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide, dimethylsulfoxide or dimethylacetamide may be exemplified, but are not limited thereto. After formation of the random copolymer, the random copolymer can be obtained by precipitation using a non-solvent. Non-solvents that can be used at this time include alcohols such as methanol, ethanol, n-propanol or isopropanol, ethylene glycol, etc. Ether solvents such as glycol, n-hexane, cyclohexane, n-heptane, or petroleum ether may be exemplified, but are not limited thereto.

In the field of polymer synthesis, a method of preparing a polymer by performing polymerization according to a monomer forming the polymer is known, and any of the above methods may be applied to the preparation of the random copolymer of the present application.

The pinning layer composition including the random copolymer as described above may include only the random copolymer or, if necessary, other components other than the random copolymer may be appropriately included. As described above, the pinning layer composition may include the random copolymer as at least a main component. Other components that may be included with the random copolymer include, for example, an initiator such as a thermal initiator or a photoinitiator or a crosslinking agent required when the random copolymer includes the aforementioned crosslinkable functional group.

This application also relates to a pinning layer comprising the random copolymer or a method of forming the pinning layer. In this application, the term pinning layer, as described above, refers to a layer showing a higher affinity for any one block of the block copolymer compared to other blocks.

The pinning layer may be formed on an appropriate substrate. As the substrate on which the pinning layer is formed, a silicon wafer, a silicon oxide substrate, a silicon nitride substrate, or a crosslinked poly(ethylene terephthalate) (PET) film may be exemplified, but is not limited thereto.

The pinning layer may be formed as a whole on the substrate, or may be formed in a line pattern in consideration of the location and direction of a desired block copolymer. In the chemoepitaxy process, the shape of the pinning layer considering the positioning and orientation of the block copolymer is known, and all of these shapes can be applied in the present application.

The pinning layer may be formed using the above-described pinning layer composition. For example, the process of forming the pinning layer may include coating the pinning layer composition on a substrate and crosslinking the coated layer of the pinning layer composition. The method of coating the pinning layer composition on the substrate is not particularly limited, and for example, a method such as bar coating, spin coating, or comma coating may be applied, and coating by a roll-to-roll method may also be applied. there is.

In addition, the method of crosslinking the layer of the pinning layer composition is not particularly limited, and for example, a method of inducing a covalent bond between the layer and the substrate by an appropriate method or inducing a chemical crosslinking reaction within the layer etc. may be applied.

For example, when the above process is performed by heat treatment, the heat treatment may be adjusted within a range of about 100 °C to 250 °C or about 100 °C to 200 °C. In addition, the time required for the heat treatment may be changed as needed, and may be adjusted within a range of about 1 minute to 72 hours or about 1 minute to 24 hours, for example. The temperature and time of the heat treatment may be adjusted to an appropriate level in consideration of the type of functional group of the random copolymer of the pinning layer composition.

The pinning layer may have a thickness of about 2 nm to about 100 nm, for example, and in another example about 2 nm to about 50 nm. The surface uniformity of the pinning layer may be maintained within the above thickness range, the block copolymer may be properly oriented, and there may be advantages in that etching selectivity may not be impaired in a subsequent etching process.

The present application also relates to a substrate, the pinning layer formed on the substrate, and a block copolymer formed on the pinning layer and having a first block and a second block chemically distinct from the first block. It relates to a laminate comprising a polymer film.

As described above, the pinning layer may be formed in a line pattern on the above-mentioned substrate.

In the above-described laminate, the polymer membrane can be used for various purposes, for example, various electronic or electronic devices, the process of forming the pattern, or a magnetic storage recording medium, a recording medium such as a flash memory, or a biosensor or a separator. It can be used in manufacturing processes and the like.

In one example, the block copolymer in the polymer membrane may implement a periodic structure including a sphere, a cylinder, a gyroid, or a lamellar through self-assembly. . Among the structures, in the case of spheres or lamellas, the block copolymer may exist in a vertically aligned state.

For example, in the block copolymer, within the segments of the first or second blocks or other blocks covalently bonded thereto, other segments may be vertically oriented while forming a regular structure such as a lamellar shape or a cylindrical shape.

The block copolymer that can be included in the polymer film in the above laminate is not particularly limited, but block copolymers exhibiting more appropriate orientation and positioning on the pinning layer mentioned above are the block copolymers exemplified below.

That is, in the present application, a block copolymer including a first block to be described later and a second block to be described later that is different from the first block may be applied. Each block of the block copolymer may be formed of only one type of monomer or two or more types of monomers. The block copolymer may be a diblock copolymer including only one first block and one second block. The block copolymer further includes one of each of the first and second blocks, further includes any one or both of the first and second blocks, or blocks other than the first and second blocks. It may be a block copolymer of more than triblock including additionally.

Since the block copolymer includes two or more polymer chains linked by covalent bonds, phase separation occurs and a so-called self-assembling structure is formed. The present inventors have confirmed that the block copolymer having the structure described below causes appropriate phase separation on the pinning layer described above, and excellent orientation and positioning properties are also secured.

The block copolymer of the present application may include a first block including repeating units represented by Formula 7 below and a second block including repeating units represented by Formula 8 below.

[Formula 7]

In Formula 7, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:

[Formula 8]

In Formula 8, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms.

In Formula 7, X may be an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, or -C(=O)-O- in another example, but is not limited thereto. no.

In Formula 7, P may be an arylene group having 6 to 18 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a phenylene group.

In Formula 7, Q may be connected to the para position when P is a phenylene group.

Q in Formula 7, in one example, may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O)- , For example, it may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, but is not limited thereto.

Z in Formula 7 is a hydrocarbon chain having 8 to 20 carbon atoms. In another example, the number of carbon atoms in the hydrocarbon chain may be 9 or more, 10 or more, 11 or more, or 12 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less. The hydrocarbon chain may be a straight chain hydrocarbon chain, and may be, for example, a straight chain alkyl group, an alkenyl group or an alkynyl group. The number of carbon atoms in the straight-chain alkyl group, alkenyl group or alkynyl group is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, or 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, It may be 13 or less or 12 or less.

In one example, the hydrocarbon chain is a chain including a straight chain structure, and at this time, the number of carbon atoms forming the straight chain structure may be within the range of 8 to 20. The chain may be straight or branched, but the number of carbon atoms calculated only by the number of carbon atoms forming the longest straight chain may be within the range of 8 to 20. In the case of a branched chain, the number of carbon atoms forming the straight chain structure can be calculated as the number of carbon atoms forming the longest chain. For example, when the chain is an n-pentyl group, the number of carbon atoms forming the linear structure is 5, and when the chain is a 2-methylpentyl group, the number of carbon atoms forming the linear structure is 5.

The hydrocarbon chain including the straight-chain structure may be a straight-chain or branched-chain alkyl, alkenyl, or alkynyl group, wherein the number of carbon atoms forming the straight-chain structure is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less.

In one example, one or more of the carbon atoms of the alkyl group, alkenyl group, or alkynyl group, which is the hydrocarbon chain, may be optionally replaced with a hetero atom for a carbon atom such as an oxygen atom, and at least one of the alkyl group, alkenyl group, or alkynyl group A hydrogen atom may be optionally substituted by another substituent.

In the block copolymer of the present application, the first block may consist only of repeating units comprising the units of Chemical Formula 7, or may include other repeating units in addition to the repeating units. In one example, the first block contains about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, or 90 mol% or more of repeating units of the unit of Formula 7, or , About 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or 90 mol% or less.

Types of other units that may be additionally included in the first block are not particularly limited as long as they do not adversely affect desired directionality and positioning. The unit may be, for example, a vinylpyrrolidone unit, a lactic acid unit, a vinylpyridine unit, a styrene unit such as styrene or trimethylsilylstyrene, or an ethylene oxide unit. An alkylene oxide unit, a butadiene unit, an isoprene unit, or an olefin unit such as ethylene, or a repeating unit composed of such a unit may be exemplified.

The second block having a repeating unit represented by Chemical Formula 8 exhibits excellent interaction with the first block and thus exhibits excellent directionality and positioning on the pinning layer.

In Formula 8, X ₂ may be a single bond in one example.

In Formula 8, the aryl group may be, for example, an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms, or a phenyl group.

As the halogen atom included in Chemical Formula 8, a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately exemplified, but is not limited thereto. The halogen atom may be substituted with the aryl group.

In one example, W in Formula 2 has 6 to 18 carbon atoms or 6 to 12 carbon atoms substituted with 1 or more, 2 or more, 3 or more, 4 or more or 5 or more halogen atoms (fluorine atoms or chlorine atoms, etc.) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms substituted in the above is not particularly limited, and for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms may be present.

The unit of Formula 8 may be represented by Formula 9 below in another example.

[Formula 9]

In Formula 9, X ₂ is a single bond, an oxygen atom or a sulfur atom, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms included in R ₄ to R ₈ is There may be three or more.

In Formula 9, X ₂ may be a single bond in another example.

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

The halogen atoms may be included in a haloalkyl group, and one or more, two or more, three or more, four or more, or five of R ₄ to R ₈ may be halogen atoms. In this case, the halogen atom may be a fluorine atom or a chlorine atom.

In the block copolymer, the second block may consist only of repeating units comprising the units of Chemical Formula 8 or 9, or may include other repeating units in addition to the repeating units. In one example, the second block contains about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, or 90 mol% or more of repeating units of Formula 8 or 9. or about 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or 90 mol% or less.

Types of other units that may be additionally included in the second block are not particularly limited as long as they do not adversely affect desired directionality and positioning. The unit may be, for example, a vinylpyrrolidone unit, a lactic acid unit, a vinylpyridine unit, a styrene unit such as styrene or trimethylsilylstyrene, or an ethylene oxide unit. An alkylene oxide unit, a butadiene unit, an isoprene unit, or an olefin unit such as ethylene, or a repeating unit composed of such a unit may be exemplified.

In one example, the second block may further include an alkyl styrene unit or a styrene unit together with a repeating unit represented by Formula 8 or 9. Through these additional units, a better phase separation pattern can be implemented on the pinning layer.

In the alkyl styrene unit, an alkyl group may be included in a para position, and thus the alkyl styrene unit may be a para-alkyl styrene unit.

The alkyl group included in the alkyl styrene unit may be a linear or branched chain alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

The alkyl styrene unit may be a unit in which R ₁₁ to R ₁₅ are hydrogen or an alkyl group and at least one of R ₁₁ to R ₁₅ is an alkyl group in Formula 10 below. In one example, the para-alkyl styrene unit is represented by the following formula 10 may be a unit in which R ₁₃ is an alkyl group and R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are hydrogen atoms.

The alkyl group of the alkyl styrene unit may be a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such an alkyl group may be an alkyl group of any one of R ₁₁ to R ₁₅ or an alkyl group of R ₁₃ .

Meanwhile, the styrene unit is a unit in which R ₁₁ to R ₁₅ in Formula 10 are all hydrogen.

[Formula 10]

The present inventors have confirmed that the alkyl styrene unit or the styrene unit, together with the repeating unit comprising the unit of Chemical Formula 8 or 9 in the second block, allows the second block to properly interact with the first block.

If the second block further includes a unit of Formula 10, it may include a repeating unit of Formula 8 or 9 within the range of 60 mol% to 97 mol%. In another example, the ratio may be about 65 mol% or more or 70 mol% or more, or may be 95 mol% or less, 93 mol% or less, 91 mol% or less, or 90 mol% or less.

Meanwhile, when the second block includes the alkyl styrene unit or the styrene unit, it may be included within a range of 3 mol% to 40 mol%. In other examples, the ratio is about 5 mol% or more, about 7 mol% or more, about 9 mol% or more, or about 10 mol% or more, or about 38 mol% or less, about 36 mol% or less, about 34 mol% or less, about It may be 32 mol% or less or about 30 mol% or less.

In the block copolymer, when the volume of the first block and the second block is set to 1, the volume fraction of the first block is in the range of 0.3 to 0.8, and the volume fraction of the second block is in the range of 0.2 to 0.7 can

In another example, the volume fraction of the first block may be about 0.35 or more, about 0.4 or more, or about 0.45 or more, or about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less. . In addition, the volume fraction of the second block may be about 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, or about 0.5 or more, or about 0.65 or less, about 0.6 or less, or about 0.55 or less in another example. A block copolymer including the first and second blocks in the above ratio may exhibit excellent self-assembly characteristics. The sum of the volume fractions of the first block and the second block may be 1. The volume fraction of each block of the block copolymer can be obtained based on the density of each block and the molecular weight measured by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 10,000 to 100,000. In other examples, the molecular weight (Mn) may be, for example, about 12,000 or more, 14,000 or more, 16,000 or more, 18,000 or more, about 19,000 or more, 20,000 or more, 22,000 or more, 24,000 or more, 26,000 or more, 28,000 or more, or 30,000 or more. In another example, the molecular weight (Mn) may be 95,000 or less, 90,000 or less, 85,000 or less, 80,000 or less, 75,000 or less, 70,000 or less, 65,000 or less, 60,000 or less, 55,000 or less, 50,000 or less, 45,000 or less, 40,000 or less, or 35,000 or less. . The block copolymer may have a polydispersity (Mw/Mn) within a range of 1.05 to 1.45. The degree of dispersion may be about 1.1 or more, 1.15 or more, or about 1.2 or more, or about 1.40 or less or about 1.35 or less in another example.

Within this range, the block copolymer may exhibit appropriate self-assembly characteristics. The number average molecular weight of the block copolymer may be adjusted in consideration of the desired self-assembly structure (ex. pitch of lamellar pattern, etc.).

A specific method for preparing the block copolymer as described above is not particularly limited, and, for example, the block copolymer is prepared by applying a known method for producing block copolymers using monomers capable of forming each block. can do.

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

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

In the preparation of the block copolymer, the method of forming other blocks included in the copolymer together with the block formed using the monomer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired block, and the other blocks are formed. blocks can be formed.

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

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

The living radical polymerization process is, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylform amide, dimethylsulfoxide or dimethylacetamide and the like.

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

The present application also provides a step of forming a polymer film including a self-assembled block copolymer having a first block and a second block chemically distinct from the first block on the pinning layer formed on the substrate. It relates to a method for manufacturing a laminate comprising As the block copolymer in the above, the above-described block copolymer may be used.

In the above method, a method of forming a polymer film using the block copolymer is not particularly limited. For example, the method may include forming a polymer film including the block copolymer on the pinning layer in a self-assembled state. For example, the method may include forming a layer of the block copolymer or a coating solution obtained by diluting the same in an appropriate solvent on the pinning layer by applying, and aging or heat-treating the layer, if necessary.

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

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

This application also relates to a pattern forming method. The method may include, for example, a step of selectively removing the first or second block of the block copolymer from the polymer film of the laminate and the polymer film from which the first or second block is selectively removed as a mask. A process of etching the substrate of the laminate may be included. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film including the block copolymer on a substrate, selectively removing any one or more blocks of the block copolymer present in the film, and then etching the substrate. . In this way, it is possible to form fine patterns on the nanoscale, for example. In addition, various types of patterns such as nanorods or nanoholes may be formed through the method according to the shape of the block copolymer in the polymer film. If necessary, the block copolymer and other copolymers or homopolymers may be mixed to form patterns.

For example, the method can form a nanoscale pattern of silicon oxide exhibiting a high aspect ratio. For example, after forming the polymer film on silicon oxide and selectively removing any one block of the block copolymer in a state where the block copolymer in the polymer film forms a predetermined structure, silicon oxide is formed in various ways, for example, , reactive ion etching, etc., to implement various shapes including patterns of nanorods or nanoholes. In addition, through this method, it is possible to implement a nanopattern with a large aspect ratio.

For example, the pattern may be implemented on a scale of several tens of nanometers, and such a pattern may be utilized for various purposes including, for example, a magnetic recording medium for next-generation information and electronics.

In the above method, the method of selectively removing any one block of the block copolymer is not particularly limited, and, for example, a method of removing a relatively soft block by irradiating a polymer film with appropriate electromagnetic waves, such as ultraviolet rays, etc. can be used In this case, the UV irradiation condition is determined according to the type of block of the block copolymer, and for example, it may be performed by irradiating UV light having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, a step of further removing segments decomposed by ultraviolet rays by treating the polymer film with an acid or the like may be performed following irradiation with ultraviolet rays.

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

The present application can effectively secure the desired degree of crosslinking even through a low-temperature process, can form a uniform thin film with excellent coating properties, has high adhesion to the substrate, and has low reactivity to the neutral brush layer. The branching can provide a pinning layer composition capable of forming a pinning layer.

1 to 4 are photographs showing self-assembled structures of block copolymers of Examples or Comparative Examples.

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

1. NMR measurement

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

<Applicable Abbreviations>

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

2. Gel Permeation Chromatograph (GPC)

Number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). A polymer to be measured was put in a 5 mL vial, and diluted in tetrahydro furan (THF) to a concentration of about 1 mg/mL. Subsequently, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. The analysis program used ChemStation from Agilent technologies. The elution time of the sample was compared with the calibration curve to obtain the weight average molecular weight (Mw) and number average molecular weight (Mn), respectively, and the molecular weight distribution (PDI) was calculated using the ratio (Mw/Mn). ) was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Device: 1200 series by Agilent technologies

Column: Use 2 PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1mg/mL, 200L injection

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

Preparation Example 1. Synthesis of monomer (A)

A compound of Formula A (DPM-C12) was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were put in a 250 mL flask, dissolved in 100 mL of acetonitrile, and the excess Potassium carbonate was added and reacted at 75° C. for about 48 hours under nitrogen conditions. After the reaction, the remaining potassium carbonate was removed by filtering, and acetonitrile used in the reaction was also removed. Here, a mixed solvent of DCM (dichloromethane) and water was added to work up, and the separated organic layer was collected and dehydrated by passing through MgSO ₄ . Subsequently, the target product (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) was obtained as a white solid in a yield of about 37% by column chromatography using dichloromethane (DCM).

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ6.77 (dd, 4H); δd4.45 (s, 1H); [delta]d3.89(t, 2H); δd1.75 (p, 2H); δd1.43 (p, 2H); δd1.33-1.26 (m, 16H); δd 0.88 (t, 3H).

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

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); [delta]d6.89 (dd, 2H); [delta]d6.32 (dt, 1H); [delta]d5.73 (dt, 1H); [delta]d3.94(t, 2H); [delta]d2.05 (dd, 3H); δd1.76 (p, 2H); δd1.43 (p, 2H); 1.34-1.27 (m, 16H); δd 0.88 (t, 3H).

[Formula A]

In Formula A, R is a straight-chain alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Block Copolymer

2.0 g of the monomer (A) of Preparation Example 1, 64 mg of cyanoisoprotyldithiobenzoate as a RAFT (Reversible Addition-Fragmentation chain transfer) reagent, 23 mg of AIBN (Azobisisobutyronitrile) as a radical initiator, and 5.34 mL of THF (tetrahydrofuran) was put into a 10 mL Schlenk flask, stirred at room temperature for about 1 hour under a nitrogen atmosphere, and then RAFT (Reversible Addition-Fragmentation chain transfer) polymerization was performed at 95 ° C. for 1 hour. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the large initiator was about 50% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 9,000 and 1.16, respectively.

0.3 g of the macroinitiator, 2.72 g of pentafluorostyrene monomer, and 1.3 mL of trifluorotoluene were put in a 10 mL Schlenk flask, stirred for 1 hour at room temperature under a nitrogen atmosphere, and then RAFT (Reversible Addition-Fragmentation chain transfer) polymerization reaction was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered and dried under reduced pressure to prepare a light pink block copolymer. The yield of the block copolymer was about 50% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 30,500 and 1.20, respectively. The block copolymer is a first block (volume fraction of the first block: 0.45) derived from the monomer (A) of Preparation Example 1 and a second block derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.55). Contains 2 blocks.

Preparation Example 3. Synthesis of Random Copolymer (A)

Compound of Preparation Example 1 (DPM) 3.202g, GMA (glycidyl methacrylate) 171 mg, methacrylic acid (MAA) 31 mg) and GBLMA (gamma-Butyrolactone-3-yl methacrylate) 204 mg of 77:10:10:3 After mixing to a molar ratio (DPM:GMA:MAA:GBLMA), 0.03 g of AIBN (Azobisisobutyronitrile), an initiator, was added into 2mL of THF (tetrahydrofuran), followed by free radical polymerization reaction at 60°C for 12 hours under a nitrogen atmosphere. was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a random copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the random copolymer were 37,300 g/mol and 2.86, respectively.

Preparation Examples 4 to 6. Synthesis of random copolymers

Four types of random copolymers were additionally prepared by controlling the reaction conditions so that the type and molar ratio of the applied monomers and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the random copolymer were as shown in Table 1 below. In Table 1 below, the unit of content of each monomer is mol%.

random copolymer DPM PFS GMA MAA GBLMA Mn PDI my
article
Yes 3 A 77 0 10 10 3 37.3 2.86 4 B 80 0 10 0 10 34.4 3.10 5 C 3.2 76.3 10 0.5 10 33.5 2.06 6 E 0 77 10 10 3 31.3 1.94 DPM: Compound of Formula A of Preparation Example 1
PFS: pentafluorostyrene
GMA: glycidyl methacrylate
MAA: methacrylic acid
GBLMA: gammabutyrolactone-3-yl methacrylate
Mn: number average molecular weight of random copolymer (unit: kg/mol)
PDI: Molecular Weight Distribution of Random Aerials

Preparation Example 7. Synthesis of Random Copolymer (F)

Compound of Preparation Example 1 (DPM) 1.72g, HMMA (hydroxymethyl methacrylate) 0.024 g, RAFT (Reversible Addition-Fragmentation chain Transfer) reagent (2-cyano-2-propylbenzodithioate) 10 mg, V-40 (1,1'- 6 mg of azobis (cyclohexanecarbonitrile) and 1.76 g of trifluorobenzene were put in a 10 mL Schlenk flask, stirred for approximately 30 minutes at room temperature under a nitrogen atmosphere, and RAFT (Reversible Addition- Fragmentation chain transfer) reaction was performed. After polymerization, the reaction solution was precipitated in 200 mL of methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a random copolymer. Number average molecular weight (Mn) and molecular weight of random copolymer The distributions (Mw/Mn) were 14,200 g/mol and 1.12, respectively.

Example 1.

A pinning layer crosslinked using the random copolymer (A) of Preparation Example 3 was formed on a silicon wafer to a thickness of about 9.1 nm. The pinning layer is spin-coated (3,000 rpm, 1 minute) on the silicon wafer with a coating solution prepared by dissolving the random copolymer (A) of Preparation Example 3 in a solvent (fluorobenzene) at a concentration of about 0.2% by weight, It was formed by thermal annealing for about 5 minutes at ° C. After forming the pinning layer, the substrate on which the pinning layer was formed was immersed in fluorobenzene at room temperature for about 90 seconds and then taken out. The thickness of the pinning layer before immersion was about 9.1 nm, and the thickness after immersion was about 8.5 nm. On the pinning layer, a coating solution prepared by diluting the random copolymer (F) of Preparation Example 7 in a solvent (fluorobenzene) at about 0.2% by weight was coated to a thickness of about 30 nm, and thermally aged at 160 ° C. for about 5 minutes. (thermal annealing) to form a layer. The substrate was then immersed in fluorobenzene for approximately 10 minutes. In this process, unreacted random copolymer (F) can be removed. A coating solution prepared by diluting the block copolymer prepared in Preparation Example 2 in a solvent (fluorobenzene) to about 0.2% by weight was coated on the substrate to a thickness of about 30 nm, and thermally aged at 230 ° C. for about 60 minutes ( thermal annealing) to form a block copolymer layer. As shown in FIG. 1, as a result of confirming the orientation state of the layer of the block copolymer with a scanning electron microscope (SEM) image, the horizontal orientation state of the block copolymer was confirmed. Through this, it can be inferred that the random copolymer of Preparation Example 7 does not react with the pinning layer and is mostly removed in the process using fluorobenzene.

Example 2.

A pinning layer crosslinked using the random copolymer (E) of Preparation Example 6 was formed on a silicon wafer to a thickness of about 9.7 nm. The pinning layer is spin-coated (3,000 rpm, 1 minute) on the silicon wafer with a coating solution prepared by dissolving the random copolymer (E) of Preparation Example 7 in a solvent (fluorobenzene) at a concentration of about 0.2% by weight, 200 It was formed by thermal annealing for about 5 minutes at ° C. After forming the pinning layer, the substrate on which the pinning layer was formed was immersed in fluorobenzene at room temperature for about 90 seconds and then taken out. The thickness of the pinning layer before immersion was about 9.7 nm, and the thickness after immersion was about 9.4 nm. On the pinning layer, a coating solution prepared by diluting the random copolymer (F) of Preparation Example 7 in a solvent (fluorobenzene) at about 0.2% by weight was coated to a thickness of about 30 nm, and thermally aged at 160 ° C. for about 5 minutes. (thermal annealing) to form a layer. The substrate was then immersed in fluorobenzene for approximately 10 minutes. In this process, unreacted random copolymer (F) can be removed. A coating solution prepared by diluting the block copolymer prepared in Preparation Example 2 in a solvent (fluorobenzene) to about 0.2% by weight was coated on the substrate to a thickness of about 30 nm, and thermally aged at 230 ° C. for about 60 minutes ( thermal annealing) to form a block copolymer layer. As shown in FIG. 2, as a result of confirming the orientation state of the block copolymer layer with a scanning electron microscope (SEM) image, the horizontal orientation state of the block copolymer was confirmed. Through this, it can be inferred that the random copolymer of Preparation Example 7 does not react with the pinning layer and is mostly removed in the process using fluorobenzene.

Comparative Example 1.

A crosslinked pinning layer was formed in the same manner as in Example 1 using the random copolymer (B) of Preparation Example 4, and was immersed in fluorobenzene for about 90 seconds and then taken out. In the case of Comparative Example 1, the thickness of the pinning layer before immersion was about 9.5 nm, and the thickness after immersion was about 6.8 nm, confirming that a lot of the pinning layer was lost. On the pinning layer, a coating solution prepared by diluting the random copolymer (F) of Preparation Example 7 in a solvent (fluorobenzene) at about 0.2% by weight was coated to a thickness of about 30 nm, and thermally aged at 160 ° C. for about 5 minutes. (thermal annealing) to form a layer. The substrate was then immersed in fluorobenzene for approximately 10 minutes. In this process, unreacted random copolymers (F) may be removed. A coating solution prepared by diluting the block copolymer prepared in Preparation Example 2 in a solvent (fluorobenzene) to about 0.2% by weight was coated on the substrate to a thickness of about 30 nm, and thermally aged at 230 ° C. for about 60 minutes ( thermal annealing) to form a block copolymer layer. As shown in FIG. 3, as a result of confirming the orientation state of the layer of the block copolymer with a scanning electron microscope (SEM) image, the homeotropic orientation state of the block copolymer was confirmed. Through this, it can be inferred that the random copolymer of Preparation Example 7 reacts at least partially with the pinning layer and remains without being removed in the process using fluorobenzene.

Comparative Example 2.

A crosslinked pinning layer was formed in the same manner as in Example 1 using the random copolymer (C) of Preparation Example 5, and was immersed in fluorobenzene for about 90 seconds and then taken out. On the pinning layer, a coating solution prepared by diluting the random copolymer (F) of Preparation Example 7 in a solvent (fluorobenzene) at about 0.2% by weight was coated to a thickness of about 30 nm, and thermally aged at 160 ° C. for about 5 minutes. (thermal annealing) to form a layer. The substrate was then immersed in fluorobenzene for approximately 10 minutes. In this process, unreacted random copolymers (F) may be removed. A coating solution prepared by diluting the block copolymer prepared in Preparation Example 2 in a solvent (fluorobenzene) to about 0.2% by weight was coated on the substrate to a thickness of about 30 nm, and thermally aged at 230 ° C. for about 60 minutes ( thermal annealing) to form a block copolymer layer. As shown in FIG. 4, as a result of confirming the orientation state of the block copolymer layer with a scanning electron microscope (SEM) image, the homeotropic orientation state of the block copolymer was confirmed. Through this, it can be inferred that the random copolymer of Preparation Example 7 reacts at least partially with the pinning layer and remains without being removed in the process using fluorobenzene.

Claims (16)

a unit represented by Formula 1 or Formula 2 below; a unit represented by Formula 3 below; And a random copolymer comprising a crosslinkable functional group-containing unit,
A pinning layer composition having a random copolymer containing a unit represented by Formula 3 in an amount of 3 to 20 mol%:
[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:
[Formula 2]

In Formula 2, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms:
[Formula 3]

In Formula 3, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxyl group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylene group having 1 to 4 carbon atoms to be. The pinning layer composition according to claim 1, wherein X in Formula 1 is an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-. The pinning layer composition according to claim 1, wherein the random copolymer contains a unit represented by Formula 1 or 2 in an amount of 70 mol% or more. The random copolymer according to claim 1, wherein the random copolymer includes a unit represented by Formula 1 and a unit represented by Formula 2, and is represented by Formula 1 relative to the total number of moles (A) of units represented by Formulas 1 and 2 A pinning layer composition having a ratio (B/A) of the number of moles (B) of the unit being less than 0.1 or greater than 0.24. The pinning layer composition according to claim 1, wherein the crosslinkable functional group-containing unit is represented by Formula 4 below:
[Formula 4]

In Formula 4, R ₃ is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom. The pinning layer composition according to claim 1, wherein the random copolymer contains a crosslinkable functional group-containing unit in an amount of 1 to 30 mol%. The pinning layer composition according to claim 1, wherein the random copolymer further comprises a lactone group-containing unit. The pinning layer composition according to claim 7, wherein the lactone group-containing unit is represented by the following formula (5):
[Formula 5]

In Formula 5, R ₉ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₁₀ is -L ₂ -U, wherein L ₂ is a single bond, an alkylene group having 1 to 4 carbon atoms or an oxygen atom, and U is a lactone group. to be. The pinning layer composition according to claim 7, wherein the random copolymer contains lactone group-containing units in an amount of 0.01 to 40 mol%. a unit represented by Formula 1 or Formula 2 below; a unit represented by Formula 3 below; And a random copolymer including a crosslinkable functional group-containing unit, and a pinning layer having a random copolymer including a unit represented by the following formula (3) in a ratio of 3 to 20 mol%:
[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:
[Formula 2]

In Formula 2, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms:
[Formula 3]

In Formula 3, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxyl group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylene group having 1 to 4 carbon atoms to be. A method for forming a pinning layer comprising the steps of coating the pinning layer composition of claim 1 on a substrate and crosslinking the coated layer of the pinning layer composition. Board; a pinning layer of claim 10 formed on the substrate; and a polymer film formed on the pinning layer and including a block copolymer having a first block and a second block chemically distinct from the first block. 13. The laminate according to claim 12, wherein the pinning layer is formed in a line pattern on the substrate. The laminate according to claim 12, wherein the first block of the block copolymer has repeating units represented by the following formula (7), and the second block includes repeating units represented by the following formula (8):
[Formula 7]

In Formula 7, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:
[Formula 8]

In Formula 8, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms. Lamination comprising the step of forming a polymer film comprising a self-assembled block copolymer having a first block and a second block chemically distinct from the first block on the pinning layer of claim 10 formed on the substrate. How to make a sieve. Selectively removing the first or second block of the block copolymer from the polymer film of the laminate of claim 12 and etching the substrate of the laminate using the polymer film from which the first or second block is selectively removed as a mask A pattern forming method comprising the steps.

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