KR102096270B1 - Compositon for neural layer - Google Patents

Abstract

This application relates to a neutral layer composition. In the present application, a neutral layer composition capable of forming a neutral layer that can be effectively applied to the formation of a polymer film including a vertically oriented self-assembled block copolymer may be provided.

Description

Composition of the neutral layer {COMPOSITON FOR NEURAL LAYER}

This application relates to a neutral layer composition.

With the development of technology, the size of the device is getting smaller, there is a need for a technology capable of producing a fine pattern. The photolithography method, which is a method of forming an existing pattern, has difficulty in manufacturing fine patterns of 20 nm or less due to technical limitations of light dispersion and wavelength of the light source. As an alternative, extreme ultraviolet lithography (EUV) ), Multiple patterning, nano imprint lithography (NIL), direct self-assembly (DSA), etc. have been proposed.

However, extreme ultraviolet lithography has a drawback that it is difficult to commercialize due to high-priced equipment and low productivity, and multiple patterning technology also has a problem that the process cost is high due to a long process time and thus the price of the semiconductor can be increased. In addition, the nano-imprint lithography technology has the advantage of having a lower production cost than the above technologies, but the technology has not been verified whether a fine pattern having a line width of 10 nm or less can be implemented.

Accordingly, direct self-assembly (DSA) technology, which forms a fine pattern by a self-assembly process of a block copolymer, has attracted attention. Direct self-assembly lithography can form a fine pattern with a line width of 10 nm or less through a simple process, and since the chemical structure of the material is similar to the photoresist currently used, it is easily applicable to existing production processes and has excellent productivity.

More specifically, a block copolymer having a molecular structure in which polymer blocks having different chemical structures are connected through covalent bonds can be separated into regular microphases due to self-assembly characteristics, Various nanostructures, such as spheres, cylinders, or lamellas, can be formed.

An important issue in the technique of forming a fine pattern using various nanostructures formed by the block copolymer is to control the orientation of the fine phase of the block copolymer. If the spherical block copolymer nanostructure has a 0-dimensional structure that does not have a specific orientation direction, the cylindrical or lamella-type nanostructures have orientations as 1-dimensional and 2-dimensional structures, respectively. The typical orientation of the block copolymer includes a parallel orientation in which the orientation of the nanostructure is parallel to the substrate direction, and a vertical orientation in which the orientation of the nanostructure is vertical to the substrate orientation, of which the vertical orientation is horizontal. It is often more important than orientation.

Typically, the orientation of the nanostructures in the film of the block copolymer can be determined by which of the blocks of the block copolymer is exposed to the surface or air. That is, the orientation of the nanostructures may be determined by selective wetting of the corresponding block. In general, since a plurality of substrates are polar and air is non-polar, blocks having a greater polarity in the block copolymer are wetted to the substrate. Blocks having a smaller polarity (wetting) are wetted at the interface with air, and a parallel orientation is induced.

An object of the present application is to provide a neutral layer composition capable of adjusting the orientation of the block copolymer thin film.

The above and other other objects of the present application can be achieved by the present application described in detail below.

In one example regarding the present application, the present application relates to a neutral layer composition. The term neutral layer composition in the present application may mean a composition used to form a neutral layer. Also, the term neutral layer in the present application may mean any kind of layer capable of inducing the vertical orientation of the block copolymer.

In the present application, the term alkyl group may mean 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 by one or more substituents.

In the present application, the term alkoxy group may mean 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 by one or more substituents.

The term alkenyl group or alkynyl group in the present application means an alkenyl group or an 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 linear, branched or cyclic, and may be optionally substituted by one or more substituents.

In the present application, 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 by one or more substituents.

The term alkenylene group or alkynylene group in the present application, unless specifically defined otherwise, has 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or an alkenylene group with 2 to 4 carbon atoms or an alkynylene group Can mean The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted by one or more substituents.

The term aromatic structure in the present application may mean the aryl group or arylene group. The aryl group or arylene group is a structure in which one benzene ring structure, two or more benzene rings are connected while sharing one or two carbon atoms, or are connected by any linker, unless otherwise specified. It may mean a monovalent or divalent residue derived from a compound or a derivative thereof.

In addition, the aryl group or the arylene group, unless otherwise specified, for example, may be 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. .

Terms in this application The term alicyclic ring structure in the present specification means a cyclic hydrocarbon structure that is not an aromatic ring structure, 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, unless otherwise specified. .

In the present application, the term single bond may mean a case where a separate atom does not exist at a corresponding site. For example, in the structure represented by A-B-C, when B is a single bond, there are no separate atoms at the site represented by B, and it may mean that A and C are directly connected to form a structure represented by A-C.

In the present application, as a substituent which may be optionally substituted with 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 straight chain or an aromatic structure, a hydroxy 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, alkynyl group Although a ren group, an alkoxy group, an aryl group, etc. can be illustrated, it is not limited thereto.

In one example, the neutral layer composition according to the present application includes a random copolymer comprising a unit represented by Formula 1 below.

[Formula 1]

In Formula 1, X2 represents a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -alkylene group, alkenylene group, alkynylene group, -C (= O) -X3- or -X3-C (= O)-, wherein X3 is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen, an alkyl group, It is a haloalkyl group, a halogen atom or an alkoxy group, at least one of R1 to R5 is an alkoxy group, and at least one of R1 to R5 is a halogen atom.

In one example, when X2 in Formula 1 is a single bond, X2 is not present and the benzene ring is directly connected to a carbon atom.

The neutral layer composition of the present application includes a random copolymer including a unit represented by Formula 1, various block copolymers, for example, a block of the unit of Formula 1 or a unit having a similar structure as described below. By adjusting the orientation of the block copolymer thin film including the block of, it is possible to effectively induce the vertical orientation of the block copolymer thin film, thereby enabling the implementation of a fine pattern.

The proportion of the unit represented by the formula (1) in the random copolymer is not particularly limited, and may be adjusted according to the type of the random copolymer to which the neutral layer is applied. In one example, the ratio of the unit represented by Formula 1 may be about 10 mol% to 90 mol%, but is not limited thereto. In another example, the ratio may be at least about 15 mol%, at least 20 mol%, at least 25 mol%, at least 30 mol%, at least 35 mol%, at least 40 mol%, or at least 45 mol%, and also at least 85 mol%, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, or 55 mol% or less.

In one example, at least three or more of R1 to R5 of Formula 1 are halogen atoms. The halogen atom may be exemplified by fluorine or chlorine, and more preferably a fluorine atom.

In one example, R 3 in Formula 1 may be an alkoxy group, and the alkoxy group may have 1 to 4 carbon atoms. When the alkoxy group is located in R3, the orientation of the block copolymer thin film can be effectively controlled by adjusting the surface energy of the neutral layer containing the neutral layer composition, thereby inducing the vertical orientation of the block copolymer thin film.

In one example, the random copolymer may further include a polymerization unit derived from a (meth) acrylic acid ester compound. The polymerization unit derived from the (meth) acrylic acid ester compound is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , It may be a polymerization unit derived from isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate or octyl (meth) acrylate, but is not limited thereto.

In another example, the polymerization unit derived from the (meth) acrylic acid ester compound may be represented by Chemical Formula 2.

[Formula 2]

In Formula 2, R6 is hydrogen or an alkyl group having 1 to 4 carbon atoms, Q1 is an oxygen atom, -O-L1-C (= O)-or -O-L1-, and L1 is an alkylene group having 1 to 4 carbon atoms. , X1 is an aromatic or alicyclic hydrocarbon, and Y1 is a straight chain having 8 or more chain-forming atoms.

In one example, the straight chain of Chemical Formula 2 includes 8 to 20 chain-forming atoms, and the chain-forming atoms may be carbon, oxygen, nitrogen, or sulfur. When the chain-forming atoms in the above range are included, the vertical orientation of the block copolymer may be induced by controlling the surface energy of the neutral layer including the neutral layer composition.

The ratio of the unit represented by Chemical Formula 2 in the random copolymer is not particularly limited, and may be adjusted according to the type of the random copolymer to which the neutral layer is applied. In one example, the ratio of the unit represented by Chemical Formula 2 may be about 10 mol% to 90 mol%, but is not limited thereto.

In one example, the random copolymer of the present application may further include a unit of Formula 3 below.

[Formula 3]

In Formula 3, R7 is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom. The crosslinking structure of the random copolymer can be achieved more effectively by including the unit of Chemical Formula 3.

In the above, the polymerization unit derived from a predetermined monomer may mean a skeleton structure in which each of the monomers described above is polymerized to form a random copolymer.

In one example, the copolymer may have a number average molecular weight (Mn, Number Average Molecular Weight) of 3,000 to 200,000. In other examples, the number average molecular weight is 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, 40,000 or more, 50,000 or more, 60,000 or more, 70,000 or more, 80,000 or more , 90,000 or more, or about 100,000 or more. The number average molecular weight may be about 150,000 or less, or 100,000 or less, in other examples. In the present specification, the term number average molecular weight is a conversion value for standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight means a number average molecular weight unless otherwise specified. The molecular weight of the copolymer can be adjusted in consideration of the physical properties of the neutral layer containing the random copolymer.

The method for preparing the copolymer as described above is not particularly limited. For example, the random copolymer may be prepared by applying a free radical polymerization method (LRP) or a Living Radical Polymerization (LRP) method. As an example of the LRP method, an anionic polymerization or polymerization agent in which polymerization is performed in the presence of an inorganic acid salt or an organic aluminum compound such as a salt of an alkali metal or an alkaline earth metal using an organic rare earth metal complex or an organic alkali metal compound as an initiator. ARGET (Activators Regenerated by Electron), which uses an atomic transfer radical polymerization method (ATRP) using an atomic transfer radical polymerization agent as a yesterday and an atomic transfer radical polymerization agent as a polymerization control agent, but performs polymerization under an organic or inorganic reducing agent that generates electrons. Transfer) Atomic Transfer Radical Polymerization (ATRP), Initiators for continuous activator regeneration (ICAR) Atomic Transfer Radical Polymerization, Inorganic Reducing Agent Reversible Addition-Cracked Chain Transfer Using Reversible Transfer Agent (RAFT) or Organic The method using a tellurium compound as an initiator, etc. can be illustrated. , A suitable method may be employed in the method.

The type 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 benzoyl peroxide (BPO) or di-tert-butyl peroxide (DTBP) may be applied, for example, thermal self-initiation of a styrene-based monomer (thermal self) -Initiation, a polymerization method without an initiator may be applied depending on the type of monomer.

The polymerization process, for example, can be carried out in a suitable solvent, in which case, as applicable solvents, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, anisole, acetone , A solvent such as chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide, dimethylsulfoxide or dimethylacetamide, but is not limited thereto. After the formation of the random copolymer, a random copolymer can be obtained by precipitation using a non-solvent, and as a non-solvent that can be used at this time, alcohols such as methanol, ethanol, n-propanol or isopropanol, ethylene glycol, etc. Ether-based solvents such as glycol, n-hexane, cyclohexane, n-heptane, or petroleum ether, and the like, 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 method among the above methods may be applied to the production of the random copolymer of the present application.

The neutral layer composition including the random copolymer may include only the predetermined random copolymer, or, if necessary, other components other than the random copolymer. The neutral layer composition may include the random copolymer as at least a main component. Inclusion in the main component in the present specification, the composition comprises only the random copolymer, or about 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% or more, 70% or more by solid content, It may mean a case including 75% by weight or more, 80% by weight or more, 85% by weight or more or 90% by weight or more. In another example, the ratio may be about 100% by weight or less or about 99% by weight or less. In addition, as another component that may be included with the random copolymer, for example, a thermal initiator or photoinitiator, etc., which are required when the random copolymer includes the above-mentioned photocrosslinkable or heat crosslinkable functional groups, can be exemplified.

In another example of the present application, the present application relates to a neutral layer comprising the random copolymer. The term neutral layer in the present application means a layer capable of inducing the vertical orientation of the block copolymer as described above.

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

The neutral layer may be formed using the neutral layer composition according to the present application. For example, the process of forming the neutral layer may include coating the neutral layer composition according to the present application on a substrate and fixing the coated layer of the neutral layer composition. In the above, the method of coating the neutral 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. have.

In addition, the method of fixing the layer of the neutral layer composition in the above is not particularly limited, 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. can be applied. For example, when the above process is performed by heat treatment, the heat treatment may be controlled 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 necessary, for example, it may be adjusted within a range of about 1 minute to 72 hours or about 1 minute to 24 hours. The temperature and time of the heat treatment may be adjusted to an appropriate level in consideration of the kind of functional group of the random copolymer of the neutral layer composition and the like.

The neutral layer, for example, may have a thickness of about 2 nm to 100 nm, and in another example, a thickness of about 2 nm to 50 nm. Within the thickness range, the surface uniformity of the neutral layer may be maintained, and it may be advantageous to induce vertical orientation of the block copolymer and not impair etching selectivity in the subsequent etching process.

In another example of the present application, the present application is also a neutral layer comprising the random copolymer and a second block formed on one surface of the neutral layer and chemically distinct from the first block and the first block It relates to a laminate comprising a polymer film comprising a block copolymer having a.

In the stacked body as described above, the neutral layer may adjust the orientation of the block copolymer, thereby forming a polymer film having an appropriate vertical alignment structure.

In the above-described laminate, the polymer film may 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 separation membrane. It can be used in manufacturing processes and the like.

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

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

The block copolymer that may be included in the polymer film in the laminate is not particularly limited. In one example, the block copolymer, as the first block may include a repeating unit represented by the above formula (1).

In another example of the present application, the present application also relates to a method of forming a pattern. The method may include, for example, a process of selectively removing the first or second block of the block copolymer from the polymer film of the laminate. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film containing the block copolymer on a substrate and etching the substrate after selectively removing any one or more blocks of the block copolymer present in the film. . In this way, for example, formation of a nano-scale fine pattern is possible. In addition, various types of patterns such as nanorods or nanoholes may be formed through the above 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 a pattern. The type of the substrate applied to this method is not particularly limited, and may be selected as necessary, for example, silicon oxide or the like.

For example, the above method can form a nano-scale pattern of silicon oxide exhibiting a high aspect ratio. For example, after forming the polymer film on silicon oxide and selectively removing any block of the block copolymer in a state in which the block copolymer in the polymer film forms a predetermined structure, silicon oxide is removed in various ways, for example. , Reactive ion etching can be used to implement various forms including nanorods or nanohole patterns. In addition, through this method, it may be possible to realize a nano pattern having 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 uses including, for example, magnetic recording media for next-generation information electronics.

The method of selectively removing any one block of the block copolymer in the above method is not particularly limited, and for example, a method of removing a relatively soft block by irradiating an appropriate electromagnetic wave, for example, ultraviolet light, to the polymer film. Can be used. In this case, the ultraviolet irradiation conditions are determined according to the type of block of the block copolymer, and for example, it may be performed by irradiating ultraviolet rays having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, it is also possible to perform a step of further removing the segment decomposed by ultraviolet rays by treating the polymer film with acid or the like after irradiation with ultraviolet rays.

In addition, the step of etching the substrate using the polymer film with the selectively removed block as a mask is not particularly limited, and may be performed, for example, through a reactive ion etching step using CF4 / Ar ions, etc. The step of removing the polymer film from the substrate by oxygen plasma treatment or the like may also be performed.

In the present application, a neutral layer composition capable of forming a neutral layer that can be effectively applied to the formation of a polymer film including a vertically oriented self-assembled block copolymer may be provided.

1 is an SEM image of a nano pattern according to Example 1 of the present application.
2 is an SEM image of a nano pattern according to Example 1 of the present application.
3 is an SEM image of a nano pattern according to Comparative Example 1 of the present application.
4 is an SEM image of a nano pattern according to Comparative Example 2 of the present application.

Hereinafter, the present application will be described in detail through examples. However, the protection scope of the present application is not limited by the examples described 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 with a concentration of about 10 mg / ml in a solvent for measuring NMR (CDCl ₃ ), and chemical shift was expressed in ppm.

<Applied abbreviation>

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

2.GPC (GelPermeationChromatograph)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). The analyte, such as a block copolymer of Example or Comparative Example or a macroinitiator, is added to a 5 mL vial and diluted in tetrahydro furan (THF) to a concentration of about 1 mg / mL. Then, 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. As the analysis program, ChemStation of Agilent technologies was used, and 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) at the ratio (Mw / Mn). ) Was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Instrument: 1200 series from Agilent technologies

Column: 2 PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1mg / mL, 200L injection

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

Preparation Example 1 Synthesis of Compound A (DPM-C12)

To a 250 mL flask was added 10.0 g (94.2 mmol) of hydroquinone and 23.5 g (94.2 mmol) of 1-bromododecane, dissolved in 100 mL of acetonitrile, and then excess potassium carbonate. (potassium carbonate) was added and reacted at 75 ° C. under nitrogen conditions for about 48 hours. After the reaction, the remaining potassium carbonate was filtered off and acetonitrile used for the reaction was also removed. A mixture of DCM (dichloromethane) and water was added thereto to work up, and the separated organic layers were collected and passed through MgSO ₄ to dehydrate. Subsequently, 9.8 g (35.2 mmol) of the target product (4-dodecyloxyphenol) as a white solid was obtained by using DCM (dichloromethane) in column chromatography with a yield of about 37%.

<NMR analysis results>

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); δ 1.33-1.26 (m, 16H); δ 0.88 (t, 3H).

In the flask, the synthesized 4-dodecyloxyphenol 9.8 g (35.2 mmol), methacrylic acid 6.0 g (69.7 mmol), DCC (dicyclohexylcarbodiimide) 10.8 g (52.3 mmol) and DMAP (p-dimethylaminopyridine) 1.7 g (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 the reaction was completed, the salt (urea salt) generated during the reaction was removed with a filter, and the remaining methylene chloride was also removed. In column chromatography, hexane and DCM (dichloromethane) are used as mobile phases to remove impurities, and the obtained product is recrystallized from a mixed solvent of methanol and water (1: 1 mixture) to obtain a white solid target (DPM-C12) 7.7 g ( 22.2mmol) with a yield of 63%.

<NMR analysis results>

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); δ 2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 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 Compound B Compound (ETFVB)

After adding 15.0 g (77.3 mmol) of pentaluorostyrene and 7.1 g (154.6 mmol) of ethanol to the flask, dissolved in 250 mL of THF and cooled by soaking the flask in an ice bath. Sodium hydroxide 4.0g (92.7mmol) was added to the reaction solution little by little, and the flask was taken out to room temperature and reacted overnight. After the reaction was completed, extraction was performed with water and diethyl ether, and the organic layers were collected and columned with hexane to obtain 11.7 g (53.1 mmol) of the target liquid in a free phase with a yield of 69%.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 6.33 (dd, 1H); δ 6.03 (d, 1H); δ 5.62 (d, 1H); δ 4.29 (q, 2H); δ 1.42 (t, 3H).

[Formula B]

Example  One

(1) Preparation of the neutral layer composition (A)

0.485 g of the compound of Preparation Example 1 (DPM-C12), 1.673 g of the compound of Preparation Example 2 (ETFVB), 0.142 g of the crosslinking agent (GMA), 0.033 g of AIBN, and 2.333 g of THF were placed in a 10 mL Schlenk flask at room temperature under a nitrogen atmosphere. After stirring for 30 minutes, a radical polymerization reaction was performed in a silicone oil container at 70 ° C. for 12 hours. 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 new white neutral layer composition. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 48600 and 2.68, respectively.

(2) Preparation of block copolymer (B)

Compound 1 of Preparation Example 1 (DPM-C12) 4.0 g and RAFT reagent (Reversible Addition Fragmentation chain Transfer) 2-cyano-2-propyl 4-cyanobenzodithioate 142.2 mg, AIBN (Azobisisobutyronitrile) 9.5 mg and anisole 9.69 mL Was added to a 10 mL flask (Schlenk flask) and stirred for 30 minutes at room temperature under a nitrogen atmosphere, followed by performing a RAFT (Reversible Addition Fragmentation chain Transfer) polymerization reaction at 95 ° C for 1 hour.

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 light pink giant initiator. The yield of the macroinitiator was about 80% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 7,100 and 1.16, respectively.

The synthesized macroinitiator 0.45 g, the compound of Preparation Example 2 (ETFVB) 2.7908 g, 1,1'-Azobis (cyclohexane-1-carbonitrile) 0.0015 g and trifluorotoluene (trifluorotoluene) 3.2408 g 10 mL flask (Schlenk flask) and stirred for 30 minutes at room temperature under a nitrogen atmosphere, and then subjected to a RAFT (Reversible Addition Fragmentation chain Transfer) polymerization reaction at 95 ° C for 3 hours.

After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, then filtered under reduced pressure to dry to prepare a light pink block copolymer. The yield of the block copolymer was about 50%, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 18,100 and 1.18, respectively.

The block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from the compound of Formula B (ETFVB) of Preparation Example 2.

(3) Formation of a laminate

The prepared neutral layer composition (A) was dissolved in fluorobenzene at a concentration of about 0.5% by weight, and the prepared coating solution was spin coated on a silicon wafer at a rate of 3000 rpm for 60 seconds, and then thermally heated at about 200 ° C. A crosslinked neutral layer was formed through thermal crosslinking.

After dissolving the prepared block copolymer (B) in fluorobenzene at a concentration of about 1.0% by weight, spin coating the prepared coating solution on the neutral layer at a rate of 3000 rpm for 60 seconds, and then at about 200 ° C. Through thermal annealing, a polymer film including a self-assembled block copolymer was formed.

The result of taking a scanning electron microscope (SEM) image of the formed laminate is shown in FIGS. 1 and 2.

1 to 2 are SEM images of the polymer film formed as described above. 1 and 2, it can be seen that an appropriate vertically oriented lamella structure was formed.

Comparative example  One

(1) Preparation of the neutral layer composition (C)

Except for preparing the compound of Preparation Example 2 (ETFVB), a neutral layer composition was prepared in the same manner as in Example 1.

(2) Lamination and pattern formation

Using the prepared neutral layer composition (C) and the block copolymer (B) of Example 1, a laminate was formed in the same manner as in Example 1.

The SEM image of the formed laminate is shown in FIG. 3. 3, it can be confirmed that the desired polymer film was not oriented.

Comparative example  2

Without forming a neutral layer, the block copolymer (B) of Example 1 was dissolved directly in a fluorobenzene at a concentration of about 1.0% by weight on a silicon wafer, and the prepared coating solution was placed on the neutral layer at a rate of 3000 rpm. After spin coating for 60 seconds, a film including a self-assembled block copolymer was formed through thermal annealing at about 200 ° C.

The SEM image of the formed polymer film is shown in FIG. 4. 4, it can be confirmed that the desired polymer film was not oriented.

Claims (17)

Neutral layer composition comprising a random copolymer comprising a unit represented by the formula (1):
[Formula 1]

In Formula 1, X2 represents a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -alkylene group, alkenylene group, alkynylene group, -C (= O) -X3- or -X3-C (= O)-, wherein X3 is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen, an alkyl group, It is a haloalkyl group, a halogen atom or an alkoxy group, at least one of R1 to R5 is an alkoxy group, and at least one of R1 to R5 is a halogen atom.
The method of claim 1, wherein the proportion of the unit of the formula (1) in the random copolymer is in the range of 10 mol% to 90 mol% of the neutral layer composition.
The neutral layer composition of claim 1, wherein at least three or more of R1 to R5 are halogen atoms.
The neutral layer composition according to claim 3, wherein the halogen atom is a fluorine atom.
The neutral layer composition of claim 1, wherein R3 is an alkoxy group.
The neutral layer composition according to claim 5, wherein the alkoxy group has 1 to 4 carbon atoms.
The neutral layer composition according to claim 1, wherein the random copolymer further comprises a polymerization unit derived from a (meth) acrylic acid ester compound.
The method of claim 7, wherein the (meth) acrylic acid ester compound-derived polymerization unit is a neutral layer composition represented by Formula 2:
[Formula 2]

In Formula 2, R6 is hydrogen or an alkyl group having 1 to 4 carbon atoms, Q1 is an oxygen atom, -O-L1-C (= O)-or -O-L1-, and L1 is an alkylene group having 1 to 4 carbon atoms. , X1 is an aromatic or alicyclic hydrocarbon, and Y1 is a straight chain having 8 or more chain-forming atoms.
9. The composition of claim 8, wherein the straight chain comprises 8 to 20 chain forming atoms, and the chain forming atoms are carbon, oxygen, nitrogen or sulfur.
The method of claim 1, wherein the random copolymer is a neutral layer composition further comprises a unit of formula (3):
[Formula 3]

In the formula (3), R7 is a hydrogen or alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom.
The method of claim 1, wherein the random copolymer is a neutral layer composition having a number average molecular weight in the range of 3,000 to 200,000.
Neutral layer comprising a random copolymer comprising a unit represented by the formula (1):
[Formula 1]

In Formula 1, X2 represents a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -alkylene group, alkenylene group, alkynylene group, -C (= O) -X3- or -X3-C (= O)-, wherein X3 is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen, an alkyl group, It is a haloalkyl group, a halogen atom or an alkoxy group, at least one of R1 to R5 is an alkoxy group, and at least one of R1 to R5 is a halogen atom.
Coating the neutral layer composition of claim 1 on a substrate; And
A method of forming a neutral layer comprising; fixing the layer of the coated neutral layer composition.
The neutral layer of claim 12; And
A polymer layer formed on one side of the neutral layer, the polymer film including a block copolymer having a first block and a second block that is chemically distinct from the first block.
15. The laminate of claim 14, wherein the first block of the block copolymer comprises units of formula (1):
[Formula 1]

In Formula 1, X2 is a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -alkylene group, alkenylene group, alkynylene group, -C (= O) -X3- or -X3-C (= O)-, wherein X3 is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen, an alkyl group, It is a haloalkyl group, a halogen atom or an alkoxy group, at least one of R1 to R5 is an alkoxy group, and at least one of R1 to R5 is a halogen atom.
Forming a neutral layer by coating the neutral layer composition of claim 1 on a substrate; And forming a polymer film comprising a block copolymer having a first block and a second block chemically distinct from the first block on one surface of the neutral layer in a self-assembled state. Way.
A pattern forming method comprising selectively removing the first or second block of the block copolymer from the polymer film of the laminate of claim 14.

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