KR20190052743A - Laminate - Google Patents

Abstract

The present invention relates to a laminate which can be effectively applied to the production of various patterned substrates because highly aligned block copolymers having no alignment defects, coordination number defects, and distance defects can be formed on a substrate, and to a production method of a patterned substrate using the same.

Description

Laminate {LAMINATE}

The present application relates to a laminate.

The block copolymer has a molecular structure in which polymer blocks having different chemical structures are linked via covalent bonds. The block copolymer can form a periodically arranged structure such as a sphere, a cylinder or a lamella by phase separation. The shape and size of the domain of the structure formed by the self-assembly phenomenon of the block copolymer can be extensively controlled by, for example, the kind of the monomer forming each block or the relative ratio between the blocks.

Due to these properties, the block copolymer is considered to be applied to a variety of next generation nano devices such as nanowire fabrication, quantum dots or metal dots, or to a lithography method capable of forming a high-density pattern on a predetermined substrate .

The technique of adjusting the orientation of the self-assembled structure of the block copolymer horizontally or vertically on various substrates occupies a very large proportion in the practical application of the block copolymer. Typically, the orientation of the nanostructure in the film of the block copolymer is determined by which block of the block copolymer is exposed to the surface or air. In general, since a plurality of substrates are polar and air is non-polar, a block having a larger polarity among the blocks of the block copolymer is wetted to the substrate, and a block having a smaller polarity is wetted at the interface with air ). Therefore, there is a demand for a technique for simultaneously causing the blocks having different characteristics of the block copolymer to be wetted to the substrate side.

The present application provides a laminate.

As used herein, 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.

As used herein, unless otherwise specified, 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. The alkoxy groups may be straight, branched or cyclic alkoxy groups and may optionally be substituted by one or more substituents.

As used herein, the term alkenyl 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 or alkynyl group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, unless otherwise specified, the 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. The alkylene group may be a straight, branched or cyclic alkylene group and may optionally be substituted by one or more substituents.

As used herein, the term alkenylene group or alkynylene group means an alkenylene group or 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, It can mean a group. The alkenylene or alkynylene group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, the term "aryl" group or "arylene group" means, unless otherwise specified, one benzene ring structure, two or more benzene rings connected together sharing one or two carbon atoms, Or a monovalent or di-valent residue derived from a compound or a derivative thereof. The aryl group or the 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 unless otherwise specified.

The term aromatic structure in this application may mean the aryl group or the arylene group.

As used herein, the term alicyclic ring structure means a cyclic hydrocarbon structure other than 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 .

The term single bond in the present application may mean that no separate atom is present at the site. For example, in the structure represented by A-B-C, when B is a single bond, it may mean that no atom exists at a site represented by B and A and C are directly connected to form a structure represented by A-C.

Examples of the substituent which may optionally be substituted in the present application include 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 carboxyl group, a glycidyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a thiol group, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, , An alkoxy group or an aryl group, but are not limited thereto.

The present application is directed to a laminate. The laminate of the present application may be applied to a method for producing a patterned substrate. The method of manufacturing a patterned substrate of the present application may be performed by a lithography method in which a directed self assembly material is applied as a template, and the induction self-assembled material may be a block copolymer have.

The laminated body of the present application enables the self-assembled structure of the induction self-assembled material to be formed with a higher degree of precision in the process of manufacturing the patterned substrate as described above, and thereby enables precise patterning of the substrate .

The laminate of the present application comprises: a substrate; A polymer layer including a random polymer region and a pinning region alternately arranged in a stripe form on the substrate; And a block copolymer film formed on the polymer layer.

The type of the substrate included in the laminate of the present application is not particularly limited. This substrate may be etched through a mask formed by a block copolymer film in a method of manufacturing a patterned substrate to be described later. As such a substrate, for example, various kinds of substrates requiring formation of a pattern on the surface may be used. Examples of such a substrate include semiconductor substrates such as a silicon substrate, a silicon germanium substrate, a GaAs substrate, a silicon oxide substrate, and the like. As the substrate, for example, a finert field effect transistor (finFETs) or a substrate which is applied to the formation of other electronic devices such as diodes, transistors or capacitors, etc., can be used. In addition, other materials such as ceramics may be used as the substrate according to the application, and the type of the substrate that can be applied in the present application is not limited thereto.

In this application, a stripe pattern is formed in which a random polymer region and a pinning region are alternately arranged on the surface of the substrate as described above. The stripe pattern is a pattern in which the polymer film 20 and the polymer film 30 are alternately formed on the surface of the substrate 10 to form a pattern as schematically shown in Fig. do. The polymer membrane 20 and the polymer membrane 30 may be different polymer membranes. In the stripe pattern of the laminate of the present application, for example, the plurality of random polymer regions 20 and the pinning region 30 may alternately form a stripe pattern. The random polymer region can function as a neutral region in the stripe pattern of the laminate of the present application. The present inventors have found that when the polymer stripe pattern is formed on a substrate, the orientation of the block copolymer can be controlled over a wider range than a general neutral layer. Particularly, when a plurality of random polymer regions and pinning regions are alternately formed on a substrate, even if the volume fraction of the units included in the random polymer region deviates from the range of forming a general neutral region, It was confirmed that the self assembled structure of the modified block copolymer can be formed. The neutral region in the present application may mean a region having substantially the same level of surface energy (surface tension or affinity) with respect to each of the polymer segment A and the polymer segment B which will be described later and contained in the block copolymer, ≪ / RTI > can be understood to mean a processing region known to be capable of achieving the vertical orientation of the block copolymer. The random polymer region may include a random copolymer having a unit of the following formula (1) and a unit of the following formula (2), and when the total volume of the units of the general formulas (1) and (2) is 1, the volume fraction May be in the range of 0.3 to 0.95.

 In the present application, the pinning region may be a film forming a preferential surface showing selectivity with respect to any one of the polymer segments, or may be a film formed of a pinning polymer. The selectivity in the present application means that the surface energy for the polymer segment A (or the polymer segment B) in the pinning region is lower than the surface energy for the polymer segment B (or polymer segment A), and the polymer segment A Or the polymer segment B) is preferentially contacted. In other words, it may mean that the polymer segment A (or polymer segment B) has a preferential wettability. The pinning region may refer to any kind of layer capable of imparting directionality and positioning properties to the orientation structure of the self-assembled structure of the block copolymer.

A block copolymer film is formed on the surface of the substrate on which the stripe pattern is formed as described above. The block copolymer in the block copolymer film forms a self-assembled structure. The type of the self-assembled structure formed by the block copolymer is not particularly limited and may be a known self-assembled structure, for example, a structure such as a sphere, a cylinder or a lamella, May be a lamellar structure.

In the above, the term block copolymer film may mean a film containing a block copolymer as a main component. For example, when a block copolymer contains 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more of a block copolymer on the basis of weight, the film may be referred to as a block copolymer film . The proportion of the block copolymer in the block copolymer film may be, for example, 100% or less by weight.

The block copolymer forming the block copolymer film in the laminate of the present application may include the polymer segment A and the polymer segment B different from the polymer segment A. [

The reason why the two polymer segments are the same in the present application means that the monomer units contained in any two kinds of polymer segments contain at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75% At least 80%, at least 85%, or at least 90% of the total weight of the polymer segment, and the variation of the weight ratio of the common monomer units in each polymer segment is within 30%, within 25%, within 20% Or 5% or less. Therefore, when both polymer segments do not satisfy the above conditions, they are polymer segments that are different from each other. The ratio of the monomer units common in the above may suitably be satisfied for the both polymer segment modes. For example, if one polymer segment 1 has monomer units of A, B, C, D and F and the other polymer segment 2 has monomer units of D, F, G and H, then polymer segments 1 and 2 The common proportions are 40% (= 100 x 2/5) because two common monomers are D and F in the case of polymer segment 1, and two of the five monomers are common in the case of polymer segment 1. In the case of polymer segment 2, Is 50% (= 100 x 2/5). Thus, in this case, both polymer segments may be regarded as not identical, since the common ratio is greater than 50% in polymer segment 2 alone. On the other hand, the deviation of the weight ratio of the common monomer in the above is a percentage of a numerical value obtained by dividing a value obtained by subtracting a small weight ratio from a large weight ratio by a small weight ratio. For example, in the above case, the weight ratio of the D monomer units of the segment 1 is about 40% based on the total weight percentage of the total monomer units of the segment 1, and the weight ratio of the D monomer units of the segment 2 is the whole of the segment 2 If the weight ratio of the monomer units is about 30% based on the total 100%, the weight ratio variation may be about 33% (= 100 x (40-30) / 30). When two or more monomer units common to two segments are used, in order to be the same segment, if the weight ratio deviation within 30% is satisfied with respect to all the common monomers, or if the monomer unit as the main component is satisfied, Can be considered. Each polymer segment recognized as being the same by the above criteria may be a polymer of a different type (for example, one segment is in the form of a block copolymer and the other segment is in the form of a random copolymer) Suitably it may be a polymer of the same type.

Each of the polymer segments of the block copolymer may be formed of only one type of monomer, or may be formed of two or more types of monomers. The block copolymer may be a diblock copolymer containing only one polymer segment A and one polymer segment B. [ The block copolymer may further include one or more of the polymer segments A and B, and may further include any one or both of the polymer segments A and B, or may further include another polymer segment other than the polymer segments A and B May be a block copolymer of more than the included tree block.

Since the block copolymer contains two or more polymer segments linked by covalent bonds, phase separation occurs and forms a so-called self-assembled structure. The present inventors have confirmed that the block copolymer can be more effectively applied in the laminate by satisfying any one or two or more of the conditions described below. Accordingly, the block copolymer of the present application may satisfy at least one of the following conditions. The conditions described below are in parallel, and any one condition does not override the other conditions. The block copolymer may satisfy any one of the following conditions, or may satisfy two or more conditions. The block copolymer can exhibit the vertical orientation in the above-described laminate by satisfying any one of the conditions described below. The term vertical orientation in the present application indicates the orientation of the block copolymer, and the orientation of the phase separation structure or the self-assembled structure formed by the block copolymer may mean an orientation perpendicular to the direction of the substrate. For example, The interface between the domain formed by the polymer segment A of the copolymer and the domain formed by the polymer segment B is perpendicular to the surface of the substrate. The term vertical in the present application is an expression in consideration of an error, and may mean an error including, for example, errors within ± 10 degrees, ± 8 degrees, ± 6 degrees, ± 4 degrees, or ± 2 degrees.

The absolute value of the difference between the surface energy of the polymer segment A of the block copolymer and the surface energy of the polymer segment B of the block copolymer of the present application may be 10 mN / m or less. The absolute value of the difference between the surface energy of the polymer segment A and the surface energy of the polymer segment B may be 10 mN / m or less, 9 mN / m or less, 8 mN / m or less, 7.5 mN / m or less or 7 mN / have. The absolute value of the difference in surface energy may be 1.5 mN / m, 2 mN / m or 2.5 mN / m or more. The structure in which the polymer segments A and B having the absolute value of the difference in surface energy in this range are connected by a covalent bond can induce an effective microphase seperation. The polymer segment A may be, for example, a polymer segment having a side chain as described later.

Surface energy can be measured using a Drop Shape Analyzer (DSA100, KRUSS). Specifically, the surface energy of a sample solution (block copolymer or homopolymer) to be measured is diluted with fluorobenzene to a solid concentration of about 2% by weight, and the coating solution is applied to the substrate with a thickness of about 50 nm and a coating area of 4 cm ² (Length: 2 cm, length: 2 cm), which is then dried at room temperature for about 1 hour and then thermally annealed at 160 ° C for about 1 hour. The process of dropping the deionized water whose surface tension is known in the film subjected to thermal aging and obtaining the contact angle is repeated 5 times to obtain an average value of the obtained five contact angle values and similarly, The process of dropping the known diiodomethane and determining the contact angle thereof is repeated five times, and an average value of the obtained five contact angle values is obtained. Thereafter, the surface energy can be obtained by substituting the value (Strom value) of the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angle with the deionized water and diiodo methane obtained. The numerical value of the surface energy for each polymer segment of the block copolymer can be obtained by the method described above for a homopolymer produced only of the monomer forming the polymer segment.

When the block copolymer includes a side chain as described later, the polymer segment including the side chain may have a higher surface energy than the other polymer segment. For example, if the polymer segment A of the block copolymer comprises a side chain chain, the polymer segment A may have a higher surface energy than the polymer segment B. In this case, the surface energy of the polymer segment A may be in the range of about 20 mN / m to 40 mN / m. The surface energy of the polymer segment A may be at least 22 mN / m, at least 24 mN / m, at least 26 mN / m, or at least 28 mN / m. The surface energy of the polymer segment A may be 38 mN / m or less, 36 mN / m or less, 34 mN / m or 32 mN / m or less. A block copolymer containing such a polymer segment A and exhibiting a difference in surface energy from the polymer segment B as described above can exhibit excellent self-assembling properties.

The purity of the block copolymer of the present application may be at least 80% by weight. The purity of the block copolymer is preferably 80% by weight or more based on the weight of the block copolymer, based on 100% by weight of all the polymer components (homopolymer, block copolymer and random copolymer, etc.) in the block copolymer film. It can mean something. The purity of the block copolymer is at least 80 wt%, at least 82 wt%, at least 84 wt%, at least 86 wt%, at least 88 wt%, at least 90 wt%, at least 92 wt%, at least 94 wt% , Not less than 98% by weight or not less than 99% by weight. The upper limit of the purity of the block copolymer may be, for example, 100%. When the purity of the block copolymer to be applied to the laminate of the present application satisfies the above range, defects in the self-assembling structure of the block copolymer can be minimized. The method for controlling the purity of the block copolymer is not particularly limited, and a known method for purifying the polymer may be used. For example, a method of precipitating using a solvent capable of selectively solubilizing only a homopolymer formed from a polymer segment forming the prepared block copolymer, a method of purifying a block copolymer using column chromatography or the like But is not limited thereto. The solvent used for the precipitation using the solvent is not particularly limited and includes, for example, tetrahydrofuran (THF), triethylamine (TEA), dimethylformamide (DMF), ethyl Ethylacetate or dimethyl sulfoxide (DMSO), isooctane (IO), methylene chloride (MC) and / or acetonitrile (ACN) Can be mixed and used.

Exemplary block copolymers of the present application comprise a polymer segment A and a polymer segment B different from the polymer segment A, wherein the block copolymer or the polymer segment A is in the range of -80 占 폚 to 200 占 폚 A melt transition peak or an isotropic transition peak (condition 1).

An exemplary block copolymer of the present application, the polymer segment A and the polymeric segment A than the segment contains a different polymer B, and wherein the block copolymer is the polymer or segment A, 0.5 nm ^-1 to 10 nm upon XRD ^{analysis 1} > (condition 2) within the range of 0.2 to 0.9 nm < ^-1 > within the range of the scattering vector (q) of ¹ .

Exemplary block copolymers of the present application include a polymer segment A and a polymer segment B different from the polymer segment A, wherein the polymer segment A comprises a side chain, and the number of chain-forming atoms of the side chain ) And the scattering vector (q) obtained by XRD analysis of the polymer segment A can satisfy the following equation (Condition 3).

[Equation 1]

3 nm ^-1 to 5 nm ^-1 = nq / (2 x π)

In Formula 1, n is the number of chain-forming atoms of the sidechain chain, and q is the smallest scattering vector (q) in which the peak is observed in the X-ray diffraction analysis for the polymer segment containing the sidechain chain, (Q) where the peak of the peak area is observed.

An exemplary block copolymer of the present application, the polymer segment A and the polymeric segment A than contain other polymer segment B, and the absolute value of the difference between the density of the polymer segment A and the polymeric segment B is 0.25 g / cm ³ be at least (Condition 4).

In each of the block copolymers, the polymer segment A may be a polymer segment including a side chain as described later.

Hereinafter, each of the above conditions will be described in detail.

In the present specification, physical properties such as density and the like that can be changed by temperature are values measured at room temperature unless otherwise specified. The term ambient temperature is a natural, non-warmed and non-warmed temperature, and can refer to a temperature of about 10 ° C to 30 ° C, about 25 ° C, or about 23 ° C.

A. Condition 1

Any polymer segment of the block copolymer or the block copolymer of the present application has a melting transition peak or an isotropic transition in the range of -80 ° C to 200 ° C in DSC (differential scanning calorimetry) Peak. ≪ / RTI > Any one of the polymer segments of the block copolymer or the block copolymer may exhibit either one of the peaks from the melt transition peak or the isotropic transition peak, or both peaks. Such a block copolymer may be a copolymer including a polymer segment which represents a crystal phase and / or a liquid crystal phase suitable for self-assembly, or a polymer segment which exhibits such a crystal phase and / or a liquid crystal phase. The polymer segment satisfying the condition 1 may be the polymer segment A.

Any polymer segment of the block copolymer or the block copolymer thereof exhibiting the DSC behavior described above may be satisfactorily satisfied under the following conditions.

For example, the difference (Ti-Tm) between the temperature (Ti) at which the isotropic transition peak appears and the temperature (Tm) at which the melting transition peak appears when the isotropic transition peak and the melt transition peak appear simultaneously is in the range of 5 to 70 Lt; 0 > C. In another example, the difference (Ti-Tm) is at least 10 ° C, at least 15 ° C, at least 20 ° C, at least 25 ° C, at least 30 ° C, at least 35 ° C, at least 40 ° C, at least 45 ° C, Or 60 < 0 > C or higher. The block copolymer having a difference (Ti-Tm) between the temperature (Ti) of the isotropic transition peak and the temperature (Tm) of the melt transition peak within the above range or the block copolymer comprising such a polymer segment has excellent phase separation or self- Can be maintained.

In another example, when the isotropic transition peak and the melt transition peak appear simultaneously, the ratio (M / I) of the area (I) of the isotropic transition peak and the area (M) of the melting transition peak is in the range of 0.1 to 500 Can be. In the DSC analysis, the block copolymer having the ratio (M / I) of the area (I) of the isotropic transition peak to the area (M) of the melt transition peak within the above range or the block copolymer comprising such a polymer segment has a phase separation or self- Can be maintained excellent. The ratio (M / I) may be 0.5 or more, 1 or more, 1.5 or more, 2 or more, 2.5 or more, or 3 or more in another example. In another example, the ratio M / I may be 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, 90 or less or 85 or less.

The manner of performing the DSC analysis is known, and in the present application, the above analysis can be performed by this known method.

The range of the temperature (Tm) at which the melting transition peak appears may range from -10 ° C to 55 ° C. In another example, the temperature Tm is in the range of 50 占 폚 or less, 45 占 폚 or less, 40 占 폚 or less, 35 占 폚 or less, 30 占 or less, 25 占 or less, 20 占 or 15 占 or 10 占 or 5 占 or It may be 0 ° C or less.

The block copolymer may include a polymer segment having a side chain chain as described below. In this case, the block copolymer may satisfy the following formula (2).

[Equation 2]

10 ° C ≤ Tm - 12.25 ° C × n + 149.5 ° C ≤ 10 ° C

In the formula (2), Tm is a temperature at which a melt transition peak of the block copolymer or the polymer segment having the side chain chain appears, and n is the number of chain forming atoms of the side chain.

The block copolymer satisfying the above formula may have excellent phase separation or self-assembling properties.

Tm-12.25 占 폚 占 n + 149.5 占 폚 in Formula 2 may be -8 占 폚 to 8 占 폚, -6 占 폚 to 6 占 폚, or about -5 占 폚 to 5 占 폚 in another example.

B. Condition 2

The block copolymer of the present application may include a polymer segment showing at least one peak within a predetermined range of the scattering vector (q) in XRD analysis (X-ray diffraction analysis, X-ray diffraction analysis). The polymer segment satisfying the condition 2 may be the polymer segment A.

For example, any one of the polymer segments of the block copolymer may exhibit at least one peak within the range of scattering vector (q) of 0.5 nm ^-1 to 10 nm ^-1 in X-ray diffraction analysis. The scattering vector q at which the peak appears may be 0.7 nm ^-1 or more, 0.9 nm ^-1 or more, 1.1 nm ^-1 or more, 1.3 nm ^-1 or 1.5 nm ^-1 or more in another example. In another example, the scattering vector q at which the peak appears may be 9 nm ^-1 or less, 8 nm ^-1 or less, 7 nm ^-1 or less, 6 nm ^-1 or less, 5 nm ^-1 or less, 4 nm ^-1 or less, 3.5 nm ^-1 or 3 nm ^-1 or less. The full width at half maximum (FWHM) of the peak identified within the range of the scattering vector (q) may be in the range of 0.2 to 0.9 nm ^-1 . The half width may be at least 0.25 nm ^{-1, at} least 0.3 nm ^-1, or at least 0.4 nm ^-1 in other examples. The half bandwidth may be 0.85 nm ^-1 or less, 0.8 nm ^-1 or 0.75 nm ^-1 or less in other examples.

In condition 2, the term half-width can mean the width of the peak (the difference in the scattering vector q) at the position showing the intensity of 1/2 of the intensity of the maximum peak.

The scattering vector (q) and the half width in the XRD analysis are numerical values obtained by a numerical analytical method using the minimum left-hand method as a result of XRD analysis described later. In this method, a portion showing the smallest intensity in the XRD diffraction pattern is taken as a baseline, and the intensity of the XRD pattern peak is set to a Gaussian fitting, and then the scattering vector and the full width at half maximum can be obtained from the fitted results. The R square at the time of Gaussian fitting is at least 0.9, at least 0.92, at least 0.94, or at least 0.96. The manner of obtaining the above information from the XRD analysis is known, and for example, a numerical analysis program such as an origin can be applied.

The polymer segment showing the peak of the half-width within the range of the scattering vector (q) may include a crystalline portion suitable for self-assembly. A block copolymer comprising a polymer segment identified within the range of the above-described scattering vector (q) may exhibit excellent self-assembling properties.

XRD analysis can be performed by passing the X-rays through the sample and measuring the scattering intensity according to the scattering vector. The XRD analysis can be performed using any polymer segment of the block copolymer, for example, a polymer prepared by polymerizing only the monomer constituting the polymer segment A. [ An XRD analysis can be performed on such a polymer without special pretreatment, for example, by drying the polymer under appropriate conditions and then passing it through X-rays. An X-ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm can be applied. A 2D diffraction pattern that is scattered in the sample is obtained as an image by using a measuring device (for example, 2D marCCD), and the obtained diffraction pattern is fitted in the above-described manner to obtain a scattering vector and a half width.

C. Condition 3

The block copolymer of the present application may comprise a polymer segment having a side chain chain to be described later as a polymer segment A and the number (n) of chain forming atoms of the side chain chain is measured in the same manner as in the above- The scattering vector q obtained by the X-ray diffraction analysis and the following formula 1 can be satisfied.

[Equation 1]

3 nm ^-1 to 5 nm ^-1 = nq / (2 x π)

In the formula 1, n is the number of the chain-forming atoms and q is the smallest scattering vector (q) in which the peak is observed in the X-ray diffraction analysis for the polymer segment including the side chain chain, or the largest peak area (Q) at which the peak is observed. In Equation (1),? Represents the circularity.

The scattering vector or the like introduced into the formula (1) is a value obtained by the method mentioned in the above-mentioned X-ray diffraction analysis method.

The scattering vector q introduced in Equation 1 may be, for example, a scattering vector q within a range of 0.5 nm ^-1 to 10 nm ^-1 . In another example, the scattering vector q introduced into Equation 1 may be 0.7 nm ^-1 or more, 0.9 nm ^-1 or more, 1.1 nm ^-1 or more, 1.3 nm ^-1 or 1.5 nm ^-1 or more. In another example, the scattering vector q introduced into the above formula 1 is 9 nm ^-1 or less, 8 nm ^-1 or less, 7 nm ^-1 or less, 6 nm ^-1 or less, 5 nm ^-1 or less, 4 nm ^-1 or less , 3.5 nm ^-1 or less, or 3 nm ^-1 or less.

The formula (1) indicates that when a polymer composed of only a polymer segment including the side chain of the block copolymer forms a film, the distance (D) between the polymer main chains containing the side chain and the number of chain- When the number of chain-forming atoms of the side chain in the polymer having side chain chains satisfies the above-mentioned formula 1, the crystallinity represented by the side chain is increased and consequently the phase-separating property or the vertical orientation Can be greatly improved. The nq / (2 x pi) according to the above formula 1 may be 4.5 nm ^-1 or less in another example. The distance (D, unit: nm) between the polymer main chains containing the side chain chain in the above can be calculated by the equation D = 2 x? / Q where D is the interval (D, unit: nm) and < RTI ID = 0.0 > q < / RTI >

D. Condition 4

The absolute value of the difference in density between the polymer segment A and the polymer segment B in the block copolymer is at least 0.25 g / cm ^{3, at} least 0.3 g / cm ^{3, at} least 0.35 g / cm ^{3, at} least 0.4 g / cm ^3, cm < ³ >. The absolute value of the density difference may be 0.9 g / cm ³ or more, 0.8 g / cm ³ or less, 0.7 g / cm ³ or less, 0.65 g / cm ³ or less, or 0.6 g / cm ³ or less. The structure in which the polymer segment A having the absolute value of the density difference in this range and the polymer segment B are linked by the covalent bond can induce an effective microphase seperation by phase separation due to proper non-availability.

The density of each polymer segment of the block copolymer can be measured by a known buoyancy method. For example, the mass of the block copolymer in a solvent such as ethanol, which is known in mass and density in air, is analyzed The density can be measured.

In the case where one polymer segment of the block copolymer includes a side chain as described later, the polymer segment including the side chain may have a lower density than the other polymer segment. For example, if the polymer segment A of the block copolymer comprises a side chain chain, the polymer segment A may have a lower density than the polymer segment B. In this case, the density of the polymer segment A may be in the range of about 0.9 g / cm ³ to about 1.5 g / cm ³ . The density of the polymer segment A may be 0.95 g / cm < ³ > or more. The density of the polymer segment A may be 1.4 g / cm ³ or less, 1.3 g / cm ³ or less, 1.2 g / cm ³ or less, 1.1 g / cm ³ or less, or 1.05 g / cm ³ or less. Such a block copolymer containing the polymer segment A and exhibiting the density difference with the polymer segment B as described above can exhibit excellent self-assembling properties.

As described above, the block copolymer may satisfy any one of the above conditions, or may satisfy two or more of the above conditions.

In one example, the block copolymer may include a polymer segment A satisfying any one or two or more of the conditions 1 to 3 among the above conditions and a polymer segment B showing a difference in surface energy according to the above condition 4 .

Although not limited by theory, the polymer segment A satisfying any one of the conditions 1 to 3 can exhibit crystallinity or liquid crystallinity, and accordingly, it is possible to form a self- ). In this state, when the polymer segment A and the polymer segment B satisfy the difference in surface energy according to Condition 4, the domains formed by the polymer segments A and B are substantially neutralized, and accordingly, the structure of the above- Lt; / RTI >

In the block copolymer, the volume fraction of the polymer segment A is in the range of 0.2 to 0.8, and the volume fraction of the polymer segment B may be in the range of 0.2 to 0.8. The sum of the volume fractions of the polymer segments A and B may be one. The block copolymer containing each of the above-mentioned segments at the above volume fractions may exhibit excellent self-assembling properties in the laminate. The volume fraction of each block of the block copolymer can be determined based on the density of each block and the molecular weight measured by GPC (Gel Permeation Chromatography).

In one example, the volume ratio (VB) of the unit of the formula (2) when the total volume of the units of the formulas (1) and (2) is 1 in the block copolymer and the ratio The ratio (VB / VR) of the volume fraction (VR) of the unit of the above formula (2) when the volume is 1 may be 2.2 or less. The ratio VB / VR may be, for example, not less than 0.70, not less than 0.75, not less than 0.80, or not less than 0.85, for example, not less than 2.20, 2.15 or less, 2.10 or less, 2.05 or less, 2.00 or 1.95 or less .

In one example, the total weight of the polymer segment A and the polymer segment B may be 80% or more based on the total block copolymer weight. The total weight of the polymer segment A and the polymer segment B may be at least 82%, at least 84%, at least 86%, at least 88%, at least 90%, at least 92%, at least 94%, at least 96% For example, 100% or less.

As other conditions, the number average molecular weight (Mn) of the block copolymer may be in the range of, for example, 3,000 to 300,000. In the present specification, the term number average molecular weight refers to a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph). In the present specification, the term molecular weight refers to a number average molecular weight unless otherwise specified. The molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000 or more, 13000 or more, or 15000 or more in other examples. In yet another example, the molecular weight (Mn) may be less than or equal to 250,000, less than or equal to 200,000, less than or equal to 180,000, less than or equal to 160,000, less than or equal to 140000, less than or equal to 120000, less than or equal to 100000, less than or equal to 90000, less than or equal to 80000, less than or equal to 70000, . The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.60. In another example, the degree of dispersion may be about 1.01 or more, about 1.02 or more, about 1.03 or more, about 1.04 or more, about 1.05 or more, about 1.06 or more, about 1.07 or about 1.08 or about 1.60 or less, about 1.55 or less, about 1.50 or less, about 1.45 or less, , 1.35 or less, 1.30 or less, 1.25 or less, or 1.20 or less, but is not limited thereto.

In this range, the block copolymer may exhibit proper self-assembling properties in the laminate. The number average molecular weight of the block copolymer and the like can be adjusted in consideration of the desired self-assembling structure and the like.

The above-mentioned conditions can be achieved, for example, by controlling the structure of the block copolymer. For example, the polymer segment A of the block copolymer that satisfies one or more of the above-mentioned conditions may comprise the side chain chain described below. The polymer segment A may include a cyclic structure, and the side chain may be substituted with the cyclic structure. The sidechain chain may be directly substituted on the ring structure or may be substituted by a suitable linker. The ring structure may be an aromatic structure or an alicyclic ring structure as described above. Such a ring structure may not contain a halogen atom. The polymer segment B contained in the block copolymer together with the polymer segment A may contain three or more halogen atoms. At this time, the polymer segment B includes a cyclic structure, and a halogen atom may be substituted for the cyclic structure. The ring structure may be an alicyclic ring structure or an aromatic structure described above.

The aromatic structure or the alicyclic ring structure may be a structure contained in the main chain of the polymer segment, or a structure in which the aromatic structure or the alicyclic ring structure is linked to the polymer segment main chain in the form of a side chain.

In one example, a block copolymer that meets one or more of the above conditions may comprise a polymer segment A comprising a sidechain chain and a polymer segment B different therefrom. In the above, the side chain may be a side chain having 8 or more chain-forming atoms as described later. The polymer segment A may be a polymer segment satisfying any one of the conditions 1 to 3 described above, satisfying at least two of the above conditions, or satisfying all of the above conditions.

In the above, the term side chain chain means a chain connected to the main chain of the polymer, and the term chain forming atom means an atom which forms the side chain chain and forms a straight chain structure of the chain. The side chain may be linear or branched, but the number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and other atoms bonded to the chain-forming atoms (for example, A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not included in the calculation. For example, in the case of a branched chain, the number of chain forming atoms may be calculated as the number of chain forming atoms forming the longest chain region. For example, when the side chain is an n-pentyl group, all of the chain-forming atoms are carbon atoms, and the number of the chain-forming atoms is 5 even when the side chain is a 2-methylpentyl group. The chain-forming atom may be exemplified by carbon, oxygen, sulfur or nitrogen, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of the chain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

In order to control the above-mentioned conditions, the polymer segment A of the block copolymer may have a chain having at least 8 chain-forming atoms connected to the side chain. In the present specification, the term chain and side chain chain may refer to the same object.

The side chain chain may be a chain containing at least 8, at least 9, at least 10, at least 11 or at least 12 chain forming atoms as mentioned above. The number of chain-forming atoms may also be not more than 30, not more than 25, not more than 20, or not more than 16. The chain forming atom may be a carbon, oxygen, nitrogen or sulfur atom, and may suitably be carbon or oxygen.

As the branched chain, a hydrocarbon chain such as an alkyl group, an alkenyl group or an alkynyl group can be exemplified. At least one of the carbon atoms of the hydrocarbon chain may be replaced by a sulfur atom, an oxygen atom or a nitrogen atom.

When the side chain is connected to the ring structure, the chain may be directly connected to the ring structure or may be connected via a linker. The linker is an oxygen atom, a sulfur _{atom, -NR 1 -, -S (=} O) 2 -, a carbonyl group, an alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - can be exemplified. In the above R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl can be date, X ₁ is a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, alkylene, alkenylene or alkynylene date Wherein R ₂ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group. Suitable linkers may be exemplified by oxygen atoms. The side chain may be connected to a ring structure such as an aromatic structure via an oxygen atom or a nitrogen atom, for example.

When a ring structure such as the above-described aromatic structure is linked to the main chain of the polymer segment in the form of a side chain, the aromatic structure may be directly connected to the main chain or may be connected via a linker. In this case, linker, oxygen atom, sulfur _{atom, -S (= O) 2 -} , a carbonyl group, an alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ - C (= O) - can be exemplified, wherein X ₁ may be a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group. Suitable linkers connecting aromatic structures to the backbone include, but are not limited to, -C (= O) -O- or -OC (= O) -.

In another example, the ring structure such as the aromatic structure contained in the polymer segment B of the block copolymer may contain one or more, two or more, three or more, four or more, or five or more halogen atoms. The number of halogen atoms may be, for example, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. Examples of the halogen atom include fluorine or chlorine, and the use of a fluorine atom may be advantageous. As described above, the polymer segment having a cyclic structure such as an aromatic structure containing a halogen atom can efficiently realize a phase separation structure through proper interaction with other polymer segments.

The polymer segment A may be, for example, a polymer segment including a unit represented by the following formula (1). The polymer segment may be a polymer segment containing a unit represented by the following formula (1) as a main component. The term " polymer segment or polymer " means that the polymer segment or polymer contains the unit in an amount of 60% or more, 70% or more, 80% or more, 90% Or a case where the unit is contained in an amount of 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 95 mol% or more.

[Chemical Formula 1]

Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, C (= O) -X ₁ - or -X ₁ -C (= O) - is, in the X ₁ is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, Y is 8 or more Is a monovalent substituent comprising a cyclic structure in which the side chain having the chain-forming atoms is linked.

When the side chain is an alkyl group, the alkyl group may contain 8 or more, 9 or more, 10 or more, 11 or 12 or more carbon atoms, and the number of carbon atoms of the alkyl group may be 30 Less than or equal to 25, less than or equal to 20, or less than or equal to 16. The alkenyl group or alkynyl group in the branched chain may contain at least 8, at least 9, at least 10, at least 11, or at least 12 carbon atoms, and the alkenyl group or alkynyl group may have at least one The number may be no greater than 30, no greater than 25, no greater than 20, or no greater than 16.

X in formula (1) may be -C (= O) O- or -OC (= O) - in another example.

In the general formula (1), Y is a substituent group containing the above-described side chain chain, and the above may be a substituent containing an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms, for example. The chain may be, for example, a straight chain alkyl group containing at least 8, at least 9, at least 10, at least 11, or at least 12 carbon atoms. The alkyl group may contain up to 30, up to 25, up to 20 or up to 16 carbon atoms. Such a chain may be directly connected to the aromatic structure or via the above-mentioned linker.

The unit of the above formula (1) of the polymer segment A may be a unit of the following formula (1-1) in another example.

[Formula 1-1]

In Formula 1-1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C (= O) -O-, P is an arylene group having 6 to 12 carbon atoms, Q is an oxygen atom, Forming side chain having 8 or more forming atoms.

In another embodiment, P may be phenylene, and in another example, Z may have from 9 to 20 carbon atoms, from 9 to 18 carbon atoms, from 9 to 16 carbon atoms, from 10 to 16 carbon atoms, from 11 to 16 carbon atoms, or from 12 to 16 carbon atoms Straight chain alkyl group. In the above, when P is phenylene, Q may be connected to the para position of the phenylene. In the above, the alkyl group, arylene group, phenylene group and side chain chain may be optionally substituted with one or more substituents.

The polymer segment B of the block copolymer may be, for example, a polymer segment containing a unit represented by the following formula (2). The polymer segment may include a unit represented by the following formula (2) as a main component.

(2)

In formula 2 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - is, in the X ₁ is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, W is an aryl group containing at least one halogen atom.

X ₂ in formula (2) may be a single bond or an alkylene group in another example.

In formula (2), the aryl group of W may be an aryl group having 6 to 12 carbon atoms, or may be a phenyl group. The aryl group or phenyl group may have one or more, two or more, three or more, four or five or more halogen atoms . The number of halogen atoms in the above may be, for example, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. As the halogen atom, a fluorine atom may be exemplified.

The unit of formula (2) may be represented by the following formula (2-1) in another example.

[Formula 2-1]

In formula ₂ 2-1 X is a single bond, oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or - X ₁ -C (= O) - is, in the X ₁ is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, R ₁ to R ₅ are hydrogen, an alkyl group, each independently, A haloalkyl group or a halogen atom, and the number of halogen atoms contained in R ₁ to R ₅ is one or more.

In the formula (2-1), R ₁ to R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or halogen, wherein the halogen may be chlorine or fluorine.

In formula (2-1), at least 2, at least 3, at least 4, at least 5 or at least 6 of R ₁ to R ₅ may contain a halogen. The upper limit of the number of halogen atoms is not particularly limited and may be, for example, 12 or less, 8 or less, or 7 or less.

As described above, the block copolymer may be a diblock copolymer containing any two of the above units, or a block copolymer containing any one or both of the two polymer segments together with other polymer segments.

The method of producing such a block copolymer is not particularly limited. The block copolymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. Examples thereof include an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator to form an alkali metal or alkaline earth metal , An anion polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an anion polymerization method using an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Atomic Transfer Radical Polymerization (ATRP), and ICAR (Atomization Transfer), which perform polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator. Initiators for continuous activator regeneration) Atom Transfer Radical Polymerization (ATRP) (RAFT) using a reversible addition-cleavage chain transfer agent using a reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied.

For example, the block copolymer can be prepared in a manner that includes polymerizing the reactants, including monomers capable of forming the polymer segment, in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization have. The production process of the polymer segment copolymer may further include, for example, a step of precipitating the polymerization product produced through the above process in the non-solvent.

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

The living radical polymerization process can be carried out in the presence of a base such as, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, Amide, dimethylsulfoxide or dimethylacetamide, and the like.

Examples of the non-solvent include ethers such as alcohols such as methanol, ethanol, n-propanol or isopropanol, glycols such as ethylene glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, But is not limited thereto.

When the block copolymer in the block copolymer film of the laminate forms a lamellar structure, the thickness of the block copolymer film can be controlled within a range of 1L to 10L. In the above, L is the pitch of the lamellar structure formed by the block copolymer.

The random copolymer contained in the random polymer region formed in contact with the block copolymer film formed by the block copolymer in the laminate of the present application forms the monomer forming the polymer segment A and the polymer segment B ≪ / RTI > The inventors of the present invention confirmed that a block copolymer having a highly aligned self-assembly structure can be obtained when the self-assembled structure is induced after contacting the random polymer region to form the block copolymer film.

Accordingly, the random copolymer may be a random copolymer containing units of the above-mentioned formula (1) or (1-1) and units of the formula (2) or (2-1). The random copolymer may contain only the above-mentioned monomer units, or may include additional units. In this random copolymer, the volume fraction of the unit of the formula (2) or (2-1) may be the same as that of the unit of the formula (2) or (2-1) when the total volume of the units of the above- The volume fraction of the unit of -1 may be 0.3 or more. In another embodiment, the volume fraction of the monomer units of Formula 2 or 2-1 may be about 0.30 or more, about 0.31 or more, about 0.32 or more, or about 0.33 or more.

In another example, the volume fraction may be about 0.95 or less, about 0.93, about 0.91, about 0.89, about 0.87, about 0.85, about 0.83, about 0.81, about 0.79, about 0.77, 0.75 or less or about 0.73 or less. When the random copolymer satisfies the above-mentioned volume fraction, the above-mentioned block copolymer can effectively form a self-assembled structure, and in particular, can form a vertically oriented lamellar structure.

The random polymer region may be a film containing a random copolymer as a main component. When the random polymer film is a main component, for example, when a random copolymer is contained in a certain film in an amount of 60% or more, 70% or more, 80% or more, 90% or more, or 95% . ≪ / RTI > The proportion of the random copolymer in the random polymer film can be, for example, 100% or less by weight.

In one example, the random copolymer may have a total weight of 70% or more of the unit of Formula 1 or 1-1 and the unit of Formula 2 or 2-1 based on the weight of the entire random copolymer. The total weight of the unit of the formula 1 or 1-1 and the unit of the formula 2 or 2-1 is 72% or more, 74% or more, 76% or more, 78% or more, 80% or more, 82% And the upper limit is not particularly limited, but may be, for example, 100% or less.

The number average molecular weight (Mn) of the random copolymer may be in the range of, for example, 3,000 to 300,000. In other examples, the molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 10,000 or more, or 11000 or more. In yet another example, the molecular weight (Mn) may be less than or equal to 250,000, less than or equal to 200,000, less than or equal to 180,000, less than or equal to 160,000, less than or equal to 140000, less than or equal to 120000, less than or equal to 100000, less than or equal to 90000, The random copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 3.60. The degree of dispersion may be about 1.05 or more or about 1.1 or more in other examples. In another example, the degree of dispersion may be about 3.5 or less, about 3.4 or less, about 3.3 or less, or about 3.2 or less.

The random polymer region formed by such a random copolymer is advantageous for forming a highly aligned block copolymer film.

The random copolymer as described above can be produced in a known manner.

In such a laminate, the thickness of the random polymer region may be 10 nm or less. The lower limit of the thickness of the random polymer region is not particularly limited. For example, the thickness may be about 0.5 nm or more or about 1 nm or more.

On the other hand, the pinning region for forming the stripe pattern in the laminate may be formed of a polymer which satisfies any one of the conditions 1 to 3 or two or more of the conditions 1 to 3, or a difference in surface energy between the polymer segment A and the polymer segment B And an absolute value of 10 mN / m or less. The difference in surface energy may be 9 mN / m or less, 8 mN / m or less, 7.5 mN / m or less or 7 mN / m or less. The absolute value of the difference in surface energy may be 1.5 mN / m, 2 mN / m or 2.5 mN / m or more.

By forming the stripe pattern by applying the pinning region as described above, it is possible to impart a directionality to the self-assembled structure of the block copolymer while the block copolymer in the laminate realizes a self-assembled structure more effectively. The kind of the polymer forming the pinning region is not particularly limited. For example, the polymer satisfying any one or two or more of the conditions 1 to 3 above may be the above-mentioned polymer segment A, and the absolute value of the difference in surface energy with respect to the polymer segment A is 10 mN / m or less The polymer may be the polymer segment B described above. Therefore, the polymer may be a polymer containing the above-described unit of the general formula (1) or (1-1) as a main component, or a polymer containing the unit of the above general formula (2) or 2-1 as a main component. In addition, one or more functional groups capable of forming a chemical bond with the above-described substrate may be substituted in the units of the above formula (1) or (1-1), or the units of the above formula (2) or (2-1). The functional group may be, for example, a hydroxy group, an epoxy group, a silyl group, or a carboxyl group, but is not limited thereto. When the polymer forming the pinning region includes a unit in which the functional group is substituted, the reactivity with the substrate is improved and the durability of the pinning region can be improved.

The number average molecular weight (Mn) of the polymer forming the pinning region may be in the range of, for example, 3,000 to 200,000. In other examples, the molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 10,000 or more, or 11000 or more. In another example, the molecular weight (Mn) may be less than or equal to 180,000, less than or equal to 160,000, less than or equal to 140000, less than or equal to 120000, less than or equal to 100000, less than or equal to 90000, less than or equal to 80000, The polymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 4.00. The degree of dispersion may be about 1.05 or more or about 1.1 or more in other examples. In other examples, the degree of dispersion may be about 3.9 or less, about 3.8 or less, about 3.7 or less, or about 3.6 or less.

The inventors of the present invention have confirmed that a highly precise self-assembled structure can be formed on a substrate by controlling the polymer stripe pattern in a structure of the laminate as described below.

For example, the shape of the polymer stripe pattern in the laminate can be controlled as follows.

In one example, when the self-assembling structure formed by the block copolymer in the block copolymer film of the laminate is a lamellar structure, the width of the pinning region of the polymer stripe pattern may be 0.3 x L or more, 0.4 x L or more or 0.5 x L or less, 2.0 x L or less, 1.6 x L or less, 1.2 x L or less, 1.0 x L or 0.8 x L or less. In the above, L is the pitch of the lamellar structure formed by the block copolymer. In the above, the width of the stripe is indicated by W in Fig. 1, for example.

In addition, the ratio (F / W) of the width W to the pitch F of the pinning region in the polymer stripe pattern may be in the range of 2 to 20. The pitch of the pinning region is a distance between the start point of one of the pinning regions and the start point of another pinning region adjacent to the start point of the pinning region, and is indicated by F in Fig. The ratio (F / W) of the width (W) to the pitch (F) of the pinning region may be 2 or more, 3 or more, 4 or 5 or more, and 20 or less, 18 or less, 16 or less, 14 or less, 12 or less Or 10 or less, but is not limited thereto.

The thickness of the polymer stripe pattern in the laminate may be 10 nm or less. The lower limit of the thickness of the polymer stripe pattern is not particularly limited. For example, the thickness may be about 0.5 nm or more or about 1 nm or more.

In one example of the present application, the absolute value of the difference between the thickness of the pinning region and the thickness of the random polymer region may be L or less. In the above, L is the pitch of the lamellar structure formed by the block copolymer. The lower limit of the absolute value of the difference between the thickness of the pinning region and the thickness of the random polymer region is not particularly limited, but may be 0 or more, for example. By forming the thickness difference between the thickness of the pinning region and the random polymer region within the above range, defects in the self-assembling structure of the block copolymer film formed on the polymer stripe pattern can be minimized.

The present application also relates to a method for producing a patterned substrate using such a laminate. The patterned substrate thus produced can be used in various electronic or electronic devices, a process of forming the pattern, a recording medium such as a magnetic storage medium, a flash memory, or a biosensor.

The manufacturing method may include forming a self-assembled block copolymer film on a polymer layer formed on a substrate and including a random polymer region and a pinning region alternately arranged in a stripe form. The block copolymer film may be formed using a material having a purity of the block copolymer of 80 wt% or more. The block copolymer film may include a polymer segment A having a unit of the above-mentioned formula (1) and a polymer segment B having a unit of the above-mentioned formula (2). Wherein the random polymer region is a random copolymer region having units of the formula (1) and the unit of the formula (2), and when the total volume of the units of the formulas (1) and (2) is 1 in the random copolymer, The volume fraction may be at least 0.3.

The block copolymer film described above can be formed using the above-mentioned block copolymer. There is no particular limitation on the method of forming the polymer film including the block copolymer on the substrate having the stripe pattern formed in the above manner and forming the self-assembled structure of the block copolymer in the polymer film.

For example, the method may include coating the block copolymer or a coating solution containing the block copolymer to form a layer, and then aging the layer. The aging process may be a thermal annealing process or a solvent annealing process.

Thermal aging can be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and can be performed at, for example, a temperature above the glass transition temperature or the phase transition temperature. The time at which such thermal aging is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed as required. The heat treatment temperature in the thermal aging process may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used. Further, the solvent aging step may be performed in a non-polar solvent and / or a polar solvent at a suitable room temperature for about 1 minute to 72 hours.

In one example, a substrate on which a stripe pattern is formed is formed by forming a random polymer region on a substrate, forming a layer of a composition to form a pinning region after removing a portion of the random polymer region formed on the substrate, Step < / RTI > The method of forming the random polymer region on the substrate is not particularly limited.

For example, the method may include a step of coating the above-mentioned random copolymer or a coating solution containing the same to form a layer, and aging the same. The aging process may be a thermal annealing process or a solvent annealing process. The thermal aging may be performed based on, for example, the phase transition temperature or the glass transition temperature of the random copolymer, and may be performed at a temperature above the glass transition temperature or the phase transition temperature, for example. The time at which such thermal aging is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed as required. The heat treatment temperature in the thermal aging process may be, for example, about 100 ° C to 250 ° C, but this can be changed in consideration of the random copolymer to be used. Further, the solvent aging step may be performed in a non-polar solvent and / or a polar solvent at a suitable room temperature for about 1 minute to 72 hours.

In this way, it is possible to form, for example, nanoscale fine polymer stripe patterns. The method of removing a portion of the random polymer region in the above method is not particularly limited. For example, a method of partially irradiating the random polymer region with an appropriate electromagnetic wave, for example, ultraviolet light, or applying a mask on the random polymer region A method of removing only a part of the random polymer region formed by irradiating ultraviolet rays or the like can be used. In this case, the ultraviolet ray irradiation conditions are determined depending on the type of the random polymer region, and can be performed, for example, by irradiating with ultraviolet light having a wavelength of about 254 nm for 1 minute to 60 minutes. In addition, the ultraviolet irradiation may be followed by a step of treating the polymer membrane with an acid or the like to further remove the random polymer region decomposed by ultraviolet rays.

The patterned substrate manufacturing method may further include the step of selectively removing any one of the polymer segments of the block copolymer having the self-assembled structure as described above.

For example, it may include a step of selectively removing the polymer segment A or B of the block copolymer from the laminate. The manufacturing method may include selectively removing one or more polymer segments of the block copolymer, and then etching the substrate. In this way, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation.

In the above method, a method of selectively removing one polymer segment of the block copolymer is not particularly limited. For example, a method of removing a relatively soft polymer segment by irradiating the polymer membrane with an appropriate electromagnetic wave, for example, ultraviolet light Method can be used. In this case, the ultraviolet ray irradiation conditions are determined depending on the type of the polymer segment of the block copolymer, and can be performed, for example, by irradiating ultraviolet light having a wavelength of about 254 nm for 1 minute to 60 minutes.

Following the ultraviolet irradiation, the polymer membrane may be treated with an acid or the like to further remove the segment decomposed by ultraviolet rays.

The step of selectively etching the substrate using the polymer membrane having the polymer segment removed as a mask is not particularly limited and may be performed by, for example, a reactive ion etching step using CF ₄ / Ar ions or the like, A step of removing the polymer membrane from the substrate by an oxygen plasma treatment or the like can also be performed.

The present application relates to a laminate capable of forming a highly aligned block copolymer having no alignment defects, coordination water defects, and distance defects on a substrate, and thus can be effectively applied to the production of various patterned substrates, and a patterned substrate Can be provided.

1 is a schematic view of a polymer stripe pattern of the present application.
2 is an SEM image of Example 1. Fig.
3 is an SEM image of Example 2. Fig.
4 is an SEM image of Comparative Example 1. Fig.
5 is an SEM image of Comparative Example 2. Fig.
6 is an SEM image of Comparative Example 3. Fig.
FIG. 7 is a diagram showing an analysis result of GIWAXS. FIG.

Hereinafter, the present application will be described in detail by way of examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

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 analytes were diluted to a concentration of about 10 mg / ml in a solvent for NMR measurement (CDCl ₃ ), and chemical shifts were expressed in ppm.

<Application Abbreviation>

br = broad signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = double triplet, q = quartet, p = octet, m = polyline.

2. Gel Permeation Chromatograph (GPC)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel Permeation Chromatography). Add a sample to be analyzed such as a block copolymer or a macroinitiator of the example or comparative example into a 5 mL vial and dilute with tetrahydrofuran (THF) to a concentration of about 1 mg / mL. After that, the calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. The analytical program used was a ChemStation from Agilent Technologies. The elution time of the sample was compared with a calibration curve to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the molecular weight distribution (PDI ) Were calculated. The measurement conditions of GPC are as follows.

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

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

3. GISAXS (Grazing Incidence Small Angle X-ray Scattering)

The GISAXS analysis was performed using a Pohang accelerator 3C beamline. The block copolymer to be analyzed was diluted with fluorobenzene to a solid concentration of about 0.7 wt% to prepare a coating solution, and the coating solution was spin-coated on the substrate to a thickness of about 5 nm. The coating area was adjusted to about 2.25 cm ² (width: 1.5 cm, length: 1.5 cm). The coated polymer membrane was dried at room temperature for about 1 hour and then thermally annealed at about 160 ° C for about 1 hour to induce a phase separation structure. Then, a film having a phase separation structure was formed. An X-ray diffraction pattern was obtained by scattering in a film with a detector (2D marCCD) after the X-ray was incident on the film at an incident angle within the range of about 0.12 to 0.23 degrees corresponding to the angle between the critical angle of the film and the critical angle of the substrate. At this time, the distance from the film to the detector was selected within a range of about 2 m to 3 m so that the self-assembly pattern formed on the film was well observed. The substrate may be a substrate having a hydrophilic surface (a silicon substrate treated with a solution of piranha and having a room temperature wetting angle of about 5 degrees relative to pure water) or a substrate having a hydrophobic surface (HMDS (hexamethyldisilazane) A silicon substrate having a recessed angle of about 60 degrees) was used.

4. XRD analysis method

The XRD analysis was performed by measuring the scattering intensity according to the scattering vector (q) by passing X-rays through the sample at the Pohang accelerator 4C beamline. As a sample, a synthesized polymer was purified without a specific pretreatment and then kept in a vacuum oven for one day to be dried. The dried polymer was used in an XRD measurement cell. For XRD pattern analysis, an X-ray with a vertical size of 0.023 mm and a horizontal size of 0.3 mm was used and a 2D marCCD was used as a detector. A scattered 2D diffraction pattern was obtained as an image. The obtained diffraction pattern was analyzed by a numerical analytical method using the minimum left - hand method to obtain information such as a scattering vector and a half width. In the analysis, an origin program was applied. A portion having the smallest intensity in the XRD diffraction pattern was taken as a baseline, and the intensity was set to be 0, The profile of the XRD pattern peak was subjected to Gaussian fitting, and the scattering vector and the half width were determined from the fitting results. The R square was at least 0.96 at the time of Gaussian fitting.

5. Measurement of surface energy

Surface energy was measured using a Drop Shape Analyzer (product of DSU100, KRUSS). The material to be measured (polymer) was diluted with flourobenzene to a solid concentration of about 2% by weight to prepare a coating solution. The coating solution was applied to a silicon wafer at a thickness of about 50 nm and a coating area of 4 cm ² : 2 cm, length: 2 cm). The coating layer was dried at room temperature for about 1 hour and then subjected to thermal annealing at about 160 ° C for about 1 hour. The process of dropping the deionized water whose surface tension is known in the film subjected to thermal aging and obtaining the contact angle thereof was repeated 5 times to obtain an average value of the obtained five contact angle values. In the same manner, the process of dropping the diiodomethane having known surface tension and determining the contact angle thereof was repeated five times, and an average value of the obtained five contact angle values was obtained. The surface energy was determined by substituting the value (Strom value) of the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angle with the deionized water and diiodo methane obtained. The numerical values of the surface energy for each polymer segment of the block copolymer were obtained by the method described above for a homopolymer made only of the monomer forming the polymer segment.

6. GIWAXS (Grazing Incidence Wide Angle X-ray Scattering)

The GIWAXS analysis was performed using a Pohang accelerator 3C beamline. The homopolymer to be analyzed was diluted with toluene (toulene) to a solids concentration of about 1% by weight to prepare a coating solution, and the coating solution was spin-coated on the substrate to a thickness of about 30 nm. The coating area was adjusted to about 2.25 cm ² (width: 1.5 cm, length: 1.5 cm). The coated polymer membrane was dried at room temperature for about 1 hour, and then subjected to thermal annealing at a temperature of about 160 DEG C for about 1 hour to form a film. An X-ray diffraction pattern was obtained by scattering in a film with a detector (2D marCCD) after the X-ray was incident on the film at an incident angle within the range of about 0.12 to 0.23 degrees corresponding to the angle between the critical angle of the film and the critical angle of the substrate. At this time, the distance from the film to the detector was selected within a range of about 0.1 m to 0.5 m so that the crystal or liquid crystal structure formed on the film was well observed. As a substrate, a silicon substrate having a room temperature wetting angle of about 5 degrees with respect to pure water was used as the piranha solution. An azimuthal angle of the diffraction pattern in the range of 12 nm ^-1 to 16 nm ^-1 in the GIWAXS spectrum, an azimuthal angle in the range of 90 to 90 degrees (the azimuth angle when the upper direction of the diffraction pattern (out-of-plane diffraction pattern) ), And the half width was obtained from the graph through Gauss fitting. Further, when half of the peak is observed at the time of Gauss fitting, a value twice as large as the half width (FWHM) is defined as the half width of the peak.

7. DSC Analysis

DSC analysis was performed using a PerkinElmer DSC800 instrument. Using the above equipment, the sample to be analyzed was heated from 25 ° C to 200 ° C at a rate of 10 ° C per minute under a nitrogen atmosphere, cooled again at a rate of -10 ° C per minute from 200 ° C to -80 ° C, And the temperature was raised to 200 ° C at a rate of 10 ° C per minute to obtain an endothermic curve. The obtained endothermic curve was analyzed to determine the temperature (melt transition temperature, Tm) or the temperature (isotropic transition temperature, Ti) indicating the isotropic transition peak indicating the melting transition peak, and the area of the peak was obtained. The temperature was defined as the temperature corresponding to the apex of each peak. The area per unit mass of each peak is defined as the area of each peak divided by the mass of the sample, and this calculation can be calculated using the program provided by the DSC equipment.

8. Purity analysis

Purity analysis was performed in the following manner. The prepared block copolymer was dissolved in a mixed solvent of tetrahydrofuran (THF) and acetonitrile (ACN) in a weight ratio of 6: 4, and then loaded into GPEC (gradient polymer elution chromatography) at a temperature of 35 ° C. Respectively. After the loading was completed, the mixed solvent was continuously changed up to 100 wt% of tetrahydrofuran (THF) and separated by components. The separated block copolymers were quantitatively analyzed with a PDA (photo diode array) detector to analyze the residual amount of homopolymer of each block remaining in the prepared block copolymer.

Production Example 1. Synthesis of monomer (A)

The monomer (DPM-C12) represented by the following formula (A) was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were placed in a 250-mL flask and dissolved in 100 mL of acetonitrile. Potassium carbonate was added and reacted at 75 占 폚 for about 48 hours under a nitrogen atmosphere. After the reaction, the remaining potassium carbonate was filtered off and acetonitrile used in the reaction was removed. A mixed solvent of DCM (dichloromethane) and water was added thereto to work up, and the separated organic layers were collected and dehydrated by passing through MgSO ₄ . Subsequently, the title compound (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as white solid was obtained in a yield of about 37% using dichloromethane in column chromatography.

&Lt; NMR analysis result >

_{^{1 H-NMR (CDCl 3)}} : δ6.77 (dd, 4H); [delta] 4.45 (s, 1H); [delta] 3.89 (t, 2H); [delta] 1.75 (p, 2H); [delta] 1.43 (p, 2H); [delta] 1.33-1.26 (m, 16H); [delta] 0.88 (t, 3H).

(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) , 13.9 mmol), 120 mL of methylene chloride was added, and the reaction was allowed to proceed at room temperature under nitrogen for 24 hours. After completion of the reaction, the salt (urea salt) produced during the reaction was filtered off and the remaining methylene chloride was removed. The resulting product was recrystallized in a mixed solvent of methanol and water (1: 1 mixture) to obtain the title compound as a white solid (compound of formula (A)) ( 7.7 g, 22.2 mmol) in 63% yield.

&Lt; NMR analysis result >

_{^{1 H-NMR (CDCl 3)}} : δ7.02 (dd, 2H); [delta] 6.89 (dd, 2H); [delta] 6.32 (dt, IH); [delta] 5.73 (dt, 1H); delta 3.94 (t, 2H); delta 2.05 (dd, 3H); delta 1.76 (p, 2H); [delta] 1.43 (p, 2H); 1.34-1.27 (m, 16H); [delta] 0.88 (t, 3H).

(A)

In formula (A), R is a straight chain alkyl group having 12 carbon atoms.

GIWAXS, XRD and DSC analysis

A homopolymer was prepared using the monomer (A) of Preparation Example 1, and GIWAXS and DSC were analyzed for the prepared homopolymer. In the above, the homopolymer was prepared by a method of synthesizing a macromonomer using the monomer (A) in the following examples. 7 shows the results of GIWAXS analysis for the homopolymer. In Fig. 7, R square (R square) was about 0.264 at the time of Gauss fitting. DSC analysis of the homopolymer showed that the polymer had a melting temperature of about -3 ° C and an isotropic transition temperature of about 15 ° C. Further, the ratio (M / I) of the sole area of the melt transition peak in the DSC analysis of the polymer (M) and the isotropic transition peak area (I) of the, was about 3.67, 12 nm to 16 nm of GIWAXS ^{-1 -} full width at half maximum of a peak in the ^first range of the scattering vector diffraction pattern azimuth of -90 degrees to -70 degrees of about 48 degrees, and 70 of the diffraction pattern of the scattering vector of 12 ^-1 nm to about 16 nm the range of ^-1 degree to GIWAXS The half width of the peak at the azimuth angle of 90 degrees was about 58 degrees. In X-ray diffraction analysis (XRD), a peak having a half-width of about 0.57 nm ^-1 was observed at a scattering vector value of 1.96 nm ^-1 .

Production Example 2. Synthesis of block copolymer (B)

2.0 g of the monomer (A) of Preparation Example 1, 64 mg of cyanoisoproyldithiobenzoate (Reversible Addition-Fragmentation chain Transfer) reagent, 23 mg of azobisisobutyronitrile (AIBN) as a radical initiator and 5.34 mL of benzene were dissolved in 10 mL of Schlenk flask and stirred at room temperature for 30 minutes under a nitrogen atmosphere. Reversible Addition-Fragmentation chain transfer (RAFT) polymerization was carried out at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to give a giant initiator of pink color. The yield of the macromonomer was about 82.6% 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 macroinitiator, 2.7174 g of pentafluorostyrene monomer and 1.306 mL of benzene were placed in a 10 mL Schlenk flask, stirred at room temperature for 30 minutes under nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) The reaction was carried out. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The yield of the block copolymer was about 19% by weight, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 30,000 and 1.19, respectively. The block copolymer includes a polymer segment A derived from the monomer (A) of Production Example 1 and having 12 chain-forming atoms (the number of carbon atoms of R in Formula A) and a polymer segment B derived from the pentafluorostyrene monomer . The volume fraction of the polymer segment A was about 0.36, and the volume fraction of the polymer segment B was about 0.64. The surface energy and density of the polymer segment A of the block copolymer were 30.83 mN / m and 1 g / cm ³ , respectively, and the surface energy and density of the polymer segment B were 24.4 mN / m and 1.57 g / cm ^3, respectively. In addition, the number 12 and the X-ray diffraction analysis when the scattering vector 0.5 nm of the chain-forming atoms of the polymeric segment A of the block ^{copolymer-scattering} peak being confirmed with the largest peak area in the range of 1 to 10 nm ^-1 The result obtained by substituting the vector value (q) into the equation nq / (2 × π) was about 3.75.

Production Example 3. Purification of Block Copolymer (C)

200 mg of the block copolymer (B) synthesized in Production Example 2 was reprecipitated twice in 6.0 mL of heptane to remove the homopolymer derived from the monomer (A) of Production Example 1. [ The precipitate obtained in the reprecipitation step was precipitated twice in a mixed solvent of tetrahydrofuran (THF, tetrahydrofuran) and acetonitrile (CAN, acetonitrile) in a weight ratio of 4: 6 to prepare a homopolymer of the pentafluorostyrene monomer Respectively. The precipitate obtained in the above re-precipitation step was reprecipitated in methanol and then filtered to obtain a purified block copolymer. The yield of the purification step was 86% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the purified block copolymer were 35,000 and 1.10, respectively. The purity of the purified block copolymer was quantitatively analyzed by a gradient polymer elution chromatography (GPEC) and a photo diode array (PDA) detector, and the purity of the purified block copolymer was found to be 99.0 wt%.

Production Example 4. Synthesis of random copolymer (D1)

1.16 g of the monomer (A) of Production Example 1, 0.90 g of pentafluorostyrene, 0.14 g of glycidyl methacrylate, 0.17 g of gamma-butyrolactone methacrylate, 0.03 g of AIBN (Azobisisobutyronitrile) and 2 mL of tetrahydrofuran (THF) were placed in a 10 mL flask (Schlenk flask), and free radical polymerization was performed at 60 캜 for 12 hours under a nitrogen atmosphere. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a random copolymer.

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the produced random copolymer (D1) were 41,100 and 2.59, respectively. When the total volume of the monomer unit and the pentafluorostyrene unit in Production Example 1 was 1 in the random copolymer (D1), the volume fraction of the monomer unit in Production Example 1 was 0.67, and the volume fraction of the pentafluorostyrene unit The volume fraction was about 0.33.

Production Example 5. Synthesis of random copolymer (D2)

0.33 g of the monomer (A) of Production Example 1, 1.36 g of pentafluorostyrene, 0.14 g of glycidyl methacrylate, 0.17 g of gamma-butyrolactone methacrylate, 0.03 g of AIBN (Azobisisobutyronitrile) and 2 mL of tetrahydrofuran (THF) were placed in a 10 mL flask (Schlenk flask), and free radical polymerization was performed at 60 캜 for 12 hours under a nitrogen atmosphere. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a random copolymer (D2).

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the produced random copolymer (D2) were 33,600 and 2.12, respectively. When the total volume of the monomer unit and the pentafluorostyrene unit in Production Example 1 was 1 in the random copolymer (D2), the volume fraction of the monomer unit in Production Example 1 was 0.28, and the volume fraction of the pentafluorostyrene unit The volume fraction was about 0.72.

Production Example 6. Synthesis of random copolymer (D3)

1.39 g of the monomer (A) of Production Example 1, 0.78 g of pentafluorostyrene, 0.14 g of glycidyl methacrylate, 0.17 g of gamma-butyrolactone methacrylate, 0.03 g of AIBN (Azobisisobutyronitrile) and 2 mL of tetrahydrofuran (THF) were placed in a 10 mL flask (Schlenk flask), and free radical polymerization was performed at 60 캜 for 12 hours under a nitrogen atmosphere. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a random copolymer (D3).

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the produced random copolymer (D3) were 50,400 and 2.69, respectively. When the total volume of the monomer unit and the pentafluorostyrene unit in Production Example 1 was 1 in the random copolymer, the volume fraction of the monomer unit of Production Example 1 was 0.74, the volume fraction of the pentafluorostyrene unit was Lt; / RTI &gt;

Production Example 7. Synthesis of random copolymer (D4)

1.55 g of pentafluorostyrene, 0.14 g of glycidyl methacrylate, 0.17 g of gamma-butyrolactone methacrylate, 0.03 g of AIBN (Azobisisobutyronitrile) as a radical initiator, and 0.15 g of tetrahydrofuran tetrahydrofuran, THF) was placed in a 10 mL flask (Schlenk flask), and free radical polymerization was carried out at 60 ° C for 12 hours in a nitrogen atmosphere. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent and then dried under reduced pressure to obtain a random copolymer (D4).

The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the produced random copolymer (D4) were 19,900 and 1.85, respectively. When the total volume of the monomer unit and the pentafluorostyrene unit in Production Example 1 was 1 in the random copolymer, the volume fraction of the monomer unit in Production Example 1 was 0, the volume fraction of the pentafluorostyrene unit was 0 Lt; / RTI &gt;

The random copolymer (D1) of Production Example 4 was coated on a silicon wafer substrate to a thickness of about 40 nm and subjected to thermal annealing at 160 DEG C for 24 hours to form a random polymer film. The substrate on which the random polymer film was formed was treated with ultrasonic dispersion in a fluorobenzene solution for about 10 minutes to remove unreacted materials.

A resist film (hydridosilsesquioxane (HSQ)) having a thickness of about 50 nm was formed on the random polymer film, and the resist film was patterned by an e-beam lithography method. After a random layer pattern was formed on the substrate by reactive ion etching (RIE), poly (pentafluorostyrene) (PPFS-OH) was coated to form a pinning polymer film, followed by thermal aging at 160 ° C. for 24 hours (thermal annealing). In order to remove unreacted materials, sonication was performed for 10 minutes on a solution of fluorobenzene. The width (W) of the formed pinning polymer film was about 15 nm, and the pitch (F) was about 90 nm.

The polymer block was formed using the purified block copolymer (C) of Production Example 3 on the substrate on which the polymer stripe pattern was formed in this manner. Specifically, a coating solution prepared by diluting the block copolymer (C) to a solid content concentration of about 1.0% by weight in fluorobenzene was spin-coated on the pattern of the substrate to a thickness of about 45 nm and dried at room temperature for about 1 hour Followed by thermal annealing at a temperature of about 160 DEG C for about 1 hour to form a self-assembled film. Scanning electron microscope (SEM) images were taken of the formed film.

2 is an SEM image of a self-assembled membrane prepared by preparing a random polymer film with D1. The self-assembled film formed a vertically oriented lamellar phase with a pitch of about 30 nm and a thickness of about 45 nm. From FIG. 2, it can be seen that one of the two domains of the self-assembled block copolymer is properly aligned along the polymer stripe pattern.

The experiment was carried out under the same conditions as in Example 1, except that the random polymer film was formed from the random copolymer (D2) of Production Example 5. 3 is an SEM image of Example 2. Fig. From FIG. 3, it can be seen that the self-assembled structure of the block copolymer is appropriately aligned in accordance with the polymer stripe pattern.

Comparative Example 1

An experiment was carried out under the same conditions as in Example 1, except that the purified block copolymer (C) of Production Example 3 was not used and the block copolymer (B) of Production Example 2 was used. The purity of the block copolymer (B) of Production Example 2 which was not purified was confirmed to be 72% by weight. 3 is an SEM image of the self-assembled membrane of Comparative Example 1; As can be seen from FIG. 4, when an unpurified block copolymer is applied, it can be seen that many alignment defects are observed in the self-assembled structure of the block copolymer as compared with Example 1.

Comparative Example 2

The experiment was carried out under the same conditions as in Example 1, except that the random polymer film was formed from the random copolymer (D3) of Preparation Example 6. 5 is an SEM image of Comparative Example 2. Fig. Referring to FIG. 5, the degree of alignment of the block copolymer was lowered compared with the example, and it was confirmed that many straight-line defects were observed.

Comparative Example 3

The experiment was carried out under the same conditions as in Example 1, except that the random polymer membrane was formed from the random copolymer (D4) of Preparation Example 7. [ 6 is an SEM image of Comparative Example 3. Fig. As can be seen from FIG. 6, the degree of alignment along the stripe pattern is smaller than that of the first embodiment, and it can be seen that there are more linear defects and alignment defects.

Claims (12)

Board; A polymer layer including a random polymer region and a pinning region alternately arranged in a stripe form on the substrate; And a block copolymer film formed on the polymer layer,
The purity of the block copolymer in the block copolymer film is 80% by weight or more,
Wherein the block copolymer comprises a polymer segment A having a unit represented by the following formula (1) and a polymer segment B having a unit represented by the following formula (2)
Wherein the random polymer region is a random copolymer region having a unit represented by the following general formula (1) and a unit represented by the following general formula (2), wherein in the random copolymer, The volume fraction being in the range of 0.3 to 0.95.
[Chemical Formula 1]

Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, C (= O) -X ₁ - or -X ₁ -C (= O) - is, in the X ₁ is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, Y is 8 or more Said side chain having a chain forming atom is a monovalent substituent comprising a linked ring structure:
(2)

In formula 2 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - is, in the X ₁ is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, W is an aryl group containing at least one halogen atom.
The laminated body according to claim 1, wherein the block copolymer has an absolute value of a surface energy difference between the polymer segment A and the polymer segment B of 10 mN / m and satisfies at least one of the following conditions 1 to 3:
Condition 1: indicates a melting transition peak or an isotropic transition peak within a range of -80 占 폚 to 200 占 폚 of the DSC analysis:
Condition 2: shows a peak within a range of half-value width of 0.2 to 0.9 nm ^-1 within a range of scattering vector (q) of 0.5 nm ^-1 to 10 nm ^-1 of XRD analysis:
Condition 3: Including a side chain chain, the number (n) of chain-forming atoms of the side chain chain satisfying the following formula (1) with the scattering vector (q) in the XRD analysis:
[Equation 1]
3 nm ^-1 to 5 nm ^-1 = nq / (2 x π)
In the formula 1, n is the number of the chain-forming atoms and q is the smallest scattering vector (q) in which the peak is observed in the X-ray diffraction analysis of the block copolymer or the scattering vector (q).
The laminate according to claim 1, wherein the block copolymer has a number average molecular weight of 3,000 to 300,000 and a molecular weight distribution of 1.01 to 1.60.
The laminate according to claim 1, wherein the block copolymer film has a lamellar structure.
The laminate according to claim 1, wherein the random copolymer has a number average molecular weight of 3,000 to 300,000 and a molecular weight distribution of 1.01 to 3.60.
The laminate according to claim 1, wherein the pinning region is a polymer region including the units of Formula (1) or (2).
The laminate according to claim 6, wherein the polymer has a number average molecular weight of 3,000 to 200,000 and a molecular weight distribution of 1.01 to 4.00.
The laminate according to claim 4, wherein the width of the pinning region is in the range of 0.3 x L to 2.0 x L, wherein L is the pitch of the lamellar structure of the block copolymer.
The laminate according to claim 4, wherein the ratio (F / W) of the width (W) to the pitch (F) of the pinning region is in the range of 2 to 20.
The laminate according to claim 4, wherein the absolute value of the difference between the thickness of the pinning region and the thickness of the random polymer region is not more than L, and L is a pitch of the lamellar structure.
Forming a self-assembled block copolymer film on a polymer layer formed on a substrate and including a random polymer region and a pinning region alternately arranged in a stripe form,
The block copolymer film is formed using a material having a purity of the block copolymer of 80 wt% or more,
Wherein the block copolymer film comprises a polymer segment A having a unit represented by the following formula (1) and a polymer segment B having a unit represented by the following formula (2)
Wherein the random polymer region is a random copolymer region having a unit represented by the following general formula (1) and a unit represented by the following general formula (2), wherein in the random copolymer, Wherein the volume fraction is in the range of 0.3 to 0.95.
[Chemical Formula 1]

Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, C (= O) -X ₁ - or -X ₁ -C (= O) - is, in the X ₁ is an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or alkynylene group, Y is 8 or more Said side chain having a chain forming atom is a monovalent substituent comprising a linked ring structure:
(2)

In formula 2 X2 is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ - C (= O) -, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group or an alkynylene group, and W is an aryl group containing at least one halogen atom.
12. The method of claim 11, further comprising: selectively removing one of the polymer segments of the block copolymer film forming the self-assembled structure; And etching the substrate using the block copolymer from which the polymer segment is removed as a mask.

Images