KR20200020231A - Preparation method of patterened substrate - Google Patents

Abstract

The present invention relates to a production method of a patterned substrate. The method is applied to for example, a production process or other uses of a device such as an electronic device and an integrated circuit, and to the production of an integrated optical system, guidance of a magnetic domain memory, and a detection pattern, a flat panel display, a liquid crystal displays (LCDs), a thin film magnetic head or an organic light emitting diode, and the like. In addition, the method can be used to build patterns on surfaces for use in the production of a discrete track medium such as the integrated circuit, a bit-patterned medium and/or a magnetic storage device such as a hard drive.

Description

Manufacturing method of a patterned board | substrate {PREPARATION METHOD OF PATTERENED SUBSTRATE}

The present application relates to a method of manufacturing a patterned substrate.

Block copolymers are copolymers in which polymer blocks having different chemical structures are connected through covalent bonds. Such block copolymers may form periodically arranged structures such as spheres, cylinders, or lamellas by phase separation. The shape and size of the domain of the structure formed by the self-assembly of the block copolymer can be controlled in a wide range by, for example, the type of the monomer forming each block or the relative ratio between the blocks.

Due to these characteristics, block copolymers are being studied for the production of various next generation nano devices such as nanowire fabrication, quantum dots, or metal dots, or for lithographic methods that can form high density patterns on predetermined substrates. (For example, refer to nonpatent literature 1 etc.).

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 practical applications of the block copolymer. Typically the orientation of the nanostructures 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, because many substrates are polar and air is non-polar, the block of the block copolymer having the higher polarity wets the substrate, and the block having the smaller polarity wets at the interface with the air. ) Therefore, various techniques have been proposed for wetting blocks having different properties of the block copolymer on the substrate side at the same time, and the most representative technique is the adjustment of the orientation to which the neutral surface fabrication is applied.

On the other hand, in the application of the lithographic method of forming a pattern on a substrate using a block copolymer, it is important to secure the straightness of the pattern (ex. Lamellar pattern) of the self-assembled block copolymer.

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

The present application provides a method of manufacturing a patterned substrate. One object of the present application is to provide a method of forming a pattern on a substrate using a self-assembled pattern of a block copolymer that is vertically oriented and excellent in straightness.

As used herein, unless otherwise specified, 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. The alkyl group may be a straight chain, branched or cyclic alkyl group, and may be optionally substituted with 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 group may be a straight chain, branched or cyclic alkoxy group, and may be optionally substituted with one or more substituents.

As used herein, the term alkenyl group or alkynyl group means an alkenyl group or alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. can do. The alkenyl group or alkynyl group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

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

As used herein, the term alkenylene group or alkynylene group is an alkenylene group or alkynylene having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified. Can mean a group. The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

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

In the present application, the term aromatic structure 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. .

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

In the present application, as the substituent which may be optionally substituted with an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, a chain or an aromatic structure, a hydroxy group, a halogen atom , Carboxyl group, glycidyl group, acryloyl group, methacryloyl group, acryloyl groupoxy, methacryloyl groupoxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group , An alkoxy group or an aryl group may be exemplified, but is not limited thereto.

Unless otherwise specified, physical properties that can be changed by temperature among the physical properties mentioned in the present application are measured at room temperature. The term room temperature is a natural, unheated or undecreased temperature, and may mean a temperature of about 10 ° C. to 30 ° C., about 25 ° C. or about 23 ° C. In addition, unless otherwise specified herein, the temperature The unit of is ° C.

The present application is directed to a method of manufacturing a patterned substrate. In one example, the manufacturing method may be performed by a lithography method in which a directed self assembly material is applied as a template. The induction self-assembly material may be a block copolymer.

The method of the present application is, for example, manufacturing processes or other uses of devices such as electronic devices and integrated circuits, such as integrated optical systems, guidance and detection patterns of magnetic domain memories, flat panel displays, liquid crystal displays (LCDs), thin film magnetic It can be applied to the manufacture of a head or an organic light emitting diode or the like. The method may also be used to build patterns on surfaces used in the manufacture of discrete track media such as integrated circuits, bit-patterned media and / or magnetic storage devices such as hard drives.

The method of manufacturing a patterned substrate of the present application may include forming a lamellar pattern of a block copolymer on a substrate having a stripe pattern formed of a plurality of polymer lines.

An example of the stripe pattern in the above is shown in FIG. 1. That is, in the present application, the term stripe pattern may be a pattern in which a plurality of polymer lines 10 are repeatedly formed on the substrate 100 at regular intervals as exemplarily shown in FIG. 1. In the above, the polymer line 10 may refer to a line shape formed using a polymer.

A polymer film including a block copolymer may be formed on the substrate 100 on which the pattern is formed, and a self-assembled pattern of the block copolymer may be formed through an annealing process or the like. The self-assembled pattern of the block copolymer formed in the method of the present application may be a lamellar pattern in one example. The method for causing the block copolymer to form a lamellar pattern is not particularly limited, and it is usually possible to form a lamellar pattern by adjusting the volume fraction of the blocks forming the block copolymer.

In the present application, the stripe pattern and the block copolymer may be controlled to ensure excellent vertical alignment and straightness of the lamellar pattern.

For example, in the present application, the pitch (F) between the plurality of polymer lines forming the stripe pattern and the ratio (F / L) of the pitch (L) of the lamellar pattern of the block copolymer may be in the range of 4.5 to 5.5. have. In the above, the pitch F between the plurality of polymer lines is a distance from a point where one polymer line 10 starts to a point where another adjacent polymer line 10 starts as shown in FIG. 1. In addition, the pitch of the lamellar pattern of the block copolymer (L) is a distance from the point where one phase starts to the point where another phase starts in a lameral pattern, and the method of specifying the pitch of such a lamellar pattern is well known. . The pitch of the lamellar pattern can be confirmed through, for example, a Fast Fourier Transform method.

In another example, the ratio F / L may be about 4.6 or more or about 4.7 or more, or about 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5.0 or less, or about 4.9 or less.

Meanwhile, the ratio (W / L) of the width W of each polymer line forming the stripe pattern (W, FIG. 1) and the pitch L of the lamellar pattern of the block copolymer may be one or more. The ratio (W / L), in another example, may be about 1.1 or more or about 1.2 or more, or about 3 or less, about 2.5 or less, about 2 or less, or about 1.5 or less.

The ratio of the spacing (difference (FW) between pitch F and width W in FIG. 1) between adjacent polymer lines among the plurality of polymer lines in the stripe pattern and the pitch L of the lamellar pattern of the block copolymer. ((FW) / L) may be 4 or less. The ratio ((FW) / L) may, in another example, be about 3.9 or less, about 3.8 or less, about 3.7 or less or about 3.6 or less, or about 1 or more, about 1.5 or more, about 2 or more, about 2.5 or more, about 3 or more or about 3.5 or more.

By forming the stripe pattern on the substrate in such a manner as described above and contacting it to form a lamellar pattern of the block copolymer described later, a lamellar pattern oriented vertically and excellent in straightness can be formed.

The width of the polymer line forming the stripe pattern may be in the range of about 15 nm to 30 nm. The width W is, in another example, at least about 16 nm, at least 17 nm, at least 18 nm, at least 19 nm, at least 20 nm, at least 21 nm, at least 22 nm or at least 23 nm, or at most about 29 nm, 28 nm. Or less, 27 nm or less, 26 nm or less, or 25 nm or less.

The pitch F of the polymer line forming the stripe pattern may be in a range of about 80 nm to 100 nm. In another example, the pitch W may be about 81 nm or more, 82 nm or more, 83 nm or more, 84 nm or more, 85 nm or more, 86 nm or more, 87 nm or more, 88 nm or more, 89 nm or more, or 90 nm or more. Or about 99 nm or less, 98 nm or less, 97 nm or less, 96 nm or less, 95 nm or less, 94 nm or less, 93 nm or less, 92 nm or less, 91 nm or less, or about 90 nm or less.

On the other hand, the length (G of FIG. 1) or the thickness of each polymer line forming the stripe pattern is not particularly limited. For example, the length of the polymer line may be determined according to the shape of the desired pattern or the size of the substrate.

In addition, the thickness of the polymer line may be in the range of about 5 nm to 20 nm.

Each polymer line as described above may be a polystyrene line. In the above, the polystyrene line means a line formed by using a polystyrene polymer. In addition, the polystyrene polymer may mean a polymer containing about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more or 90 mol% or more of styrene units. The ratio of the styrene units may be, for example, about 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or about 90 mol% or less. The styrene unit may be a polymerized unit derived from a general styrene monomer represented by Chemical Formula C ₆ H ₅ CH = CH ₂ or a polymerized unit derived from a styrene derivative monomer such as alpha-methyl styrene. It may be a polymerized unit derived from a general styrene monomer represented by C ₆ H ₅ CH═CH ₂ .

In one example, the polystyrene line may be a crosslinked polystyrene line implementing a crosslinking structure. In order to implement such a crosslinked structure, the polystyrene polymer may include a certain amount of crosslinkable functional groups. Such crosslinkable functional groups may be, for example, a hydroxy group, an epoxy group, an isocyanate group, a glycidyl group, a substituent of the formula (A), a benzoylphenoxy group, an alkenyloxycarbonyl group, a (meth) acryloyl group or an alkenyloxyalkyl group, or the like. The monomer having such a functional group can be copolymerized to the polystyrene polymer to introduce a crosslinkable functional group.

[Formula A]

In formula (A) Y is a single bond, an alkylene group, an alkenylene group or an alkynylene group, X is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group, an alkynylene group , -C (= O) -X ₁ -or -X ₁ -C (= O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, Alkenylene group or alkynylene group.

The functional group of formula (A) is a substituent in which a crosslinkable azide moiety is present at the terminal, and such functional group may be crosslinked.

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

In Formula A, X may be, in another example, a single bond, an oxygen atom, -C (= 0) -O-, or -O-C (= 0)-, but is not limited thereto.

As the unit containing the crosslinkable functional group, that is, the polymerized unit of the monomer including the crosslinkable functional group, any one of the units represented by the following formulas (B) to (E) can be exemplified.

[Formula B]

In formula (B), R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom.

[Formula C]

In formula (C), R is hydrogen or an alkyl group, A is an alkylene group, R 1 may be hydrogen, a halogen atom, an alkyl group or a haloalkyl group, and n is a number in the range of 1 to 3.

[Formula D]

In formula (D), R is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without hetero atoms.

[Formula E]

In formula (E), R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and T is a divalent hydrocarbon group with or without a hetero atom.

In other embodiments, the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such alkyl groups may be linear, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents.

In the formula (C), the haloalkyl group is an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, and the alkyl group is 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. Can be. Such haloalkyl groups may be straight, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents. In addition, examples of the halogen atom substituted with the hydrogen atom may include fluorine or chlorine.

In another example, the alkylene group of A may be an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. Such alkylene di groups may be straight, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents.

The divalent hydrocarbon group in the formulas (B) to (E) may further comprise a hetero atom, if necessary. In the above, the hetero atom is a hetero atom with respect to carbon, for example, oxygen, nitrogen or sulfur. Such hetero atoms may be included in the range of 1 to 4 in the divalent hydrocarbon group of Formulas B to E.

Examples of the monomer capable of forming the units of Formulas (B) to (E) are not particularly limited. For example, glycidyl (meth) acrylate may be exemplified as the monomer capable of forming the unit of Formula B, and 4-vinyl benzocyclo is a monomer capable of forming the unit of Formula C. Butene etc. can be illustrated, As a monomer which can form the unit of Formula D, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl (meth) acrylate, 4-isocyanatobutyl acrylate Or 4-isocyanatobutyl (meth) acrylate, etc. can be illustrated, As a monomer which can form the unit of general formula (E), hydroxymethyl acrylate, hydroxymethyl (meth) acrylate, 2-hydroxy Hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl acrylate, 3-hydroxyprop Lofil (meth) acrylate 2-hydroxybutyl acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylic Late or 6-hydroxyhexyl (meth) acrylate and the like can be exemplified, but is not limited thereto.

The ratio of the crosslinkable functional group-containing unit in the polystyrene polymer may be about 20 mol% or less, 18 mol% or less, 16 mol% or less, 14 mol% or less, 12 mol% or less, or about 10 mol% or more, and other examples. At about 0 mol%, at least 2 mol%, at least 4 mol%, at least 6 mol%, at least 8 mol%, or at least about 10 mol%, but is not limited thereto.

The polystyrene line or the crosslinked polystyrene line may include the polystyrene polymer or the crosslinked polystyrene polymer as a main component, and for example, the polymer line may include at least about 80 mol%, at least 82 mol%, 84 of the polystyrene polymer. It may comprise at least mol%, at least 86 mol%, at least 88 mol% or at least 90 mol% at least 90 wt%, at least 92 wt%, at least 94 wt%, at least 96 wt% or at least 98 wt%. The ratio may, in another example, be about 100% by weight or less or about 99% by weight or less.

The method of forming the polymer line by applying the polystyrene polymer as described above is not particularly limited. Various methods are known in the art for forming a polymer pattern, and all of these methods can be applied. For example, the polymer lines may be formed by lithography such as ArF immersion lithography or E-beam lithography (EBL). In addition, the method of crosslinking the polymer line is not particularly limited, and an appropriate method may be selected in consideration of the type of the crosslinkable functional group applied.

The substrate on which the stripe pattern is formed may be a substrate on which no processing other than the stripe pattern is performed. In one example, the substrate may be a substrate that has not been subjected to a known treatment known to achieve vertical orientation including so-called neutral surface treatment. Accordingly, the surface of the substrate to which the film containing the block copolymer is in contact may be a surface on which neutral treatment has not been performed, in which the neutral treatment has a vertical orientation in which the neutral brush layer and the like are known. It can be interpreted in the sense including the known treatment to achieve. In addition, in the present application, that a layer or film is formed in contact with a surface may mean a case where no other layer exists between the layer or the film and the surface.

That is, the surface where the stripe pattern does not exist in the substrate may be a bare surface, and the lamella pattern of the block copolymer may be formed by contacting the stripe pattern and the bare surface. In this case, the bare surface refers to the surface of the substrate itself, which has been treated separately or has no layer formed thereon.

The type of the substrate applied to the method of the present application is not particularly limited. As the substrate, for example, various kinds of substrates which require the formation of a pattern on the surface for application to each of the applications described above can all be used. As this kind of substrate, for example, a semiconductor substrate such as a silicon substrate, a silicon germanium substrate, a GaAs substrate, a silicon oxide substrate, or the like can be given. As the substrate, for example, a substrate applied to the formation of fin field effect transistors (finFETs) or other electronic devices such as diodes, transistors, or capacitors may be used. In addition, other materials, such as ceramics, may also be used as the substrate, depending on the application, and the type of substrate applicable to the present application is not limited thereto.

As described above, the self-assembled structure formed in the substrate on which the stripe pattern is formed may be a self-assembled structure of a vertically oriented block copolymer, and the alignment pattern may be a lamellar pattern. The term vertical alignment in the present application refers to the orientation of the block copolymer, and may refer to a case where the orientation direction of the self-assembly structure formed by the block copolymer is perpendicular to the substrate direction. For example, the vertical orientation may refer to a case in which each block domain of the self-assembled block copolymer is placed side by side on the substrate surface, and an interface region of the block domain is formed substantially perpendicular to the substrate surface. In the present application, the term vertical is an expression in consideration of an error, and may include, for example, an error within ± 10 degrees, ± 8 degrees, ± 6 degrees, ± 4 degrees, or ± 2 degrees.

The self-assembled structure of the block copolymer may be a lamellar pattern as described above. For example, when a block copolymer including a first block and a second block is used as the block copolymer, the other segment may be a lamellar form or the like in the segment of the first block or the other block covalently bonded thereto. The same regular structure may be formed.

As the block copolymer, various kinds of block copolymers may be applied, but as the block copolymer capable of exhibiting excellent vertical alignment and straightness on the stripe pattern as described above, the first block may include a repeating unit of a unit of Formula 1 below; A block copolymer having a second block including the repeating unit of the unit of formula 2 may be used.

[Formula 1]

In formula (1), R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, Z is a hydrocarbon chain of 8 to 20 carbon atoms:

[Formula 2]

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

The first and second blocks may each include about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, and 88 mol of repeat units of the unit of Formula 1 and units of Formula 2, respectively. % Or more, 90 mol% or more, about 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or about 90 mol% or less.

In Formula 1, X may be, in another example, an oxygen atom, a carbonyl group, -C (= 0) -O-, or -OC (= 0)-, or -C (= 0) -O-, but is not limited thereto. no.

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

In Formula 1, Q may be connected to a para position when P is a phenylene group, and a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , a carbonyl group, -C (= O) -O- or -OC (= O)-, for example, a single bond, oxygen atom, carbonyl group, -C (= 0) -O- or -OC (= 0) -yl However, it is not limited thereto.

In Formula 1, Z is a hydrocarbon chain having 8 to 20 carbon atoms. In other examples, the carbon number of the hydrocarbon chain may be 9 or more, 10 or more, 11 or more, or 12 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less. The hydrocarbon chain may be a straight chain hydrocarbon chain, for example, may be a straight chain alkyl group, alkenyl group or alkynyl group. Carbon number of the said linear alkyl group, alkenyl group, or alkynyl group is 8 or more, 9 or more, 10 or more, 11 or more or 12 or more, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less.

In one example, the hydrocarbon chain is a chain including a straight chain structure, wherein the number of carbon atoms forming the straight chain structure may be in the range of 8 to 20. The chain may be straight or branched, but the number of carbon atoms can be calculated from only the number of carbon atoms forming the longest straight chain. In addition, in the case of branched chains, the number of carbon atoms can be calculated as the number of carbon atoms forming the longest chain. For example, when the chain is an n-pentyl group, the number of carbon atoms forming a straight chain structure is five, and even when the chain is a 2-methylpentyl group, the number of carbon atoms forming a straight chain structure is five.

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

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

The second block having the repeating unit of the unit of Formula 2 may exhibit excellent interaction with the first block to implement a self-assembled structure of a block copolymer having excellent vertical alignment and straightness on the substrate.

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

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

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

In one example, W of formula 2 has 6 to 18 carbon atoms or 6 to 12 carbon atoms substituted with one or more, two or more, three or more, four or more or five halogen atoms (such as a fluorine atom or a chlorine atom) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms to be substituted is not particularly limited, and for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms may be present.

The unit of Formula 2 may be represented by the following Formula 3 in another example.

[Formula 3]

In Formula 3, X ₂ is a single bond, an oxygen atom, or a sulfur atom, R ₁ to R ₅ are each independently hydrogen, an alkyl group, a haloalkyl group, or a halogen atom, and the number of halogen atoms included in R ₁ to R ₅ is It may be three or more.

In Chemical Formula 3, X ₂ may be a single bond in another example.

In Formula 3, R ₁ to R ₅ are each independently hydrogen, an alkyl group, a haloalkyl group, or a halogen atom, and R ₁ to R ₅ are one or more, two or more, three or more, four or more, or five or more halogen atoms. For example, it may contain a fluorine atom or a chlorine atom. The halogen atoms contained in R ₁ to R ₅ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The halogen atom may be contained in a haloalkyl group, and at least one, at least two, at least three, at least four, or at least _five of R ₁ to R ₅ may be halogen atoms. In this case, the halogen atom may be a fluorine atom or a chlorine atom.

The block copolymer of the present application may be a diblock copolymer including only one of the first block and the second block, respectively, or a block copolymer of three or more blocks including three or more blocks.

When the volume of the first block and the second block in the block copolymer is 1, the volume fraction of the first block is in the range of 0.4 to 0.8, and the volume fraction of the second block is in the range of 0.2 to 0.6. Can be.

In another example, the volume fraction of the first block may be about 0.45 or more or about 0.5 or more, or about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, or about 0.55 or less. Further, in another example, the volume fraction of the second block may be about 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, or about 0.5 or more, or about 0.55 or less. The block copolymer including the first and second blocks in the ratio may exhibit excellent self-assembly characteristics on the stripe pattern described above. The sum of the volume fractions of the first block and the second block may be one. 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 Gel Permeation Chromatogrph (GPC).

The number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 10,000 to 30,000. As used herein, the term number average molecular weight is a conversion value with respect to standard polystyrene measured using a gel permeation chromatograph (GPC), and the term molecular weight herein refers to a number average molecular weight unless otherwise specified. In addition, unless otherwise specified, the unit of number average molecular weight is g / mol. The molecular weight (Mn) may be, for example, at least about 12,000, at least 14,000, at least 16,000, at least 18,000, at least 20,000, or at least 22,000. In another example, the molecular weight (Mn) may be about 28,000 or less, about 26,0000 or less, or about 24,000 or less. The block copolymer may have a dispersion degree (polydispersity, Mw / Mn) in the range of 1.01 to 1.60. In another example, the degree of dispersion may be about 1.05 or more or about 1.1 or more, or about 1.55 or less, about 1.5 or less, about 1.45 or less, about 1.4 or less, about 1.35 or less, about 1.3 or less, about 1.25 or less, or about 1.2 or less.

In this range, the block copolymer may exhibit suitable self-assembly characteristics on the above-described stripe pattern. The number average molecular weight of the block copolymer can be adjusted in view of the desired self-assembly structure (ex. Pitch of lamellar pattern, etc.).

When the block copolymer includes at least the first and second blocks, the proportion of the first block in the block copolymer, for example, the block including the chain described above, is 10 mol% to 90 mol%. May be in range.

The specific method for producing such a block copolymer is not particularly limited, and for example, the block copolymer may be manufactured by applying a known method for producing a block copolymer using a monomer capable of forming each block. can do.

For example, the block copolymer may be prepared by LRP (Living Radical Polymerization) method using the monomer. For example, an anionic polymerization or an organic alkali metal compound synthesized in the presence of an inorganic acid such as an alkali metal or a salt of an alkaline earth metal is polymerized using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator. Anion polymerization method synthesized in the presence of an organoaluminum compound using as an initiator, atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization control agent, an atom transfer radical polymerization agent as a polymerization control agent is used. Activators Regenerated by Electron Transfer (ARRP) Atomic Radical Polymerization (ATRP), Initiators for continuous activator regeneration (ICAR), and Reversible Addition of Inorganic Reductants Reversible addition-cleavage chain transfer using cleavage chain transfer agents And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

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

The method of forming the other block included in the copolymer together with the block formed using the monomer in the production of the block copolymer is not particularly limited, and the appropriate monomer is selected in consideration of the type of the desired block. Blocks can be formed.

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

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

Living radical polymerization processes are, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylform It may be carried out in a solvent such as amide, dimethyl sulfoxide or dimethylacetamide.

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

The above-described stripe pattern and the manner of forming a film on the substrate using the block copolymer are not particularly limited, and for forming a self-assembly structure, for example, it is applied to forming a polymer film on a neutral treated surface. Known methods that have been employed can be applied. For example, a polymer film may be formed by dispersing the block copolymer in a suitable solvent at a predetermined concentration to prepare a coating solution, and coating the coating solution by a known coating method such as spin coating.

If necessary, an annealing process for forming a self-assembly structure in the polymer film formed as described above may be further performed. Such annealing can be carried out, for example, by aging or heat treatment of the layer.

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

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

The method of manufacturing a patterned substrate of the present application may further include selectively removing any block from the self-assembled block copolymer of the film formed on the stripe pattern as described above. For example, if the block copolymer includes the aforementioned first block and second block, the method may include selectively removing the first or second block from the block copolymer. Through this process, for example, only blocks that are not selectively removed may exist on the substrate. The method of manufacturing the patterned substrate may also include etching the substrate after selectively removing any one or more blocks of the block copolymer as described above.

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

In addition, after the ultraviolet irradiation, the polymer film may be treated with an acid or the like to further remove the segment decomposed by the ultraviolet ray.

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

The present application relates to a method for producing a patterned substrate. The method is for example a manufacturing process or other uses of devices such as electronic devices and integrated circuits, such as integrated optical systems, guidance and detection patterns of magnetic domain memories, flat panel displays, liquid crystal displays (LCDs), thin film magnetic heads or It can be applied to the manufacture of organic light emitting diodes and the like, and is patterned on a surface for use in the manufacture of discrete track mediums, such as integrated circuits, bit-patterned media and / or magnetic storage devices such as hard drives. Can be used to build

1 is an exemplary view of a stripe pattern on a substrate on which a block copolymer is formed.
2 to 7 are photographs showing the self-assembly pattern formed in the Examples or Comparative Examples.

Hereinafter, the present application will be described in more detail with reference to Examples and Comparative Examples according to the present application, but the scope of the present application is not limited to the examples given below.

1. NMR measurement

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

<Applicable abbreviation>

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

2.Gel Permeation Chromatograph

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

<GPC measurement condition>

Instrument: 1200 series by Agilent technologies

Column: Uses 2 PLgel mixed Bs from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1 mg / mL, 200 L infusion

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

Preparation Example 1 Synthesis of Monomer (A)

The compound of formula A (DPM-C12) was synthesized in the following manner. Into a 250 mL flask, add hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol), dissolve in 100 mL acetonitrile, and remove excess Potassium carbonate was added and reacted at 75 ° C. for about 48 hours under nitrogen conditions. Remaining potassium carbonate after the reaction was filtered off and the acetonitrile used in the reaction was also removed. A mixed solvent of dichloromethane (DCM) and water was added thereto to work up, and the separated organic layers were collected and passed through MgSO ₄ to be dehydrated. Dichloromethane (DCM) was then used in column chromatography to give the title compound (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as a white solid in a yield of about 37%.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 6.77 (dd, 4H); δ 4.45 (s, 1 H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p, 2H); δ 1.33-1.26 (m, 16H); δ 0.88 (t, 3H).

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

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1 H); δ 5.73 (dt, 1 H); δ 3.94 (t, 2H); δ 2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16 H); δ 0.88 (t, 3H).

[Formula A]

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

Preparation Example 2 Synthesis of Block Copolymer (A)

5 g of Monomer (A) of Preparation Example 1, 456 mg of cyanoisoprotyldithiobenzoate as a Reversible Addition-Fragmentation Chain Transfer (RAFT) reagent, 34 mg of Azobisisobutyronitrile (AIBN) as a radical initiator and 12.8 mL of anisole 25 In a mL Schlenk flask was stirred for 30 minutes at room temperature under a nitrogen atmosphere and then subjected to RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction at 70 ℃ for 4 hours. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the macroinitiator was about 72% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 5,900 and 1.17, respectively. 1 g of macroinitiator, 8.96 g of pentafluorostyrene monomer, and 3.3 mL of anisole were added to a 25 mL Schlenk flask, stirred at room temperature for 30 minutes under nitrogen atmosphere, and then RAFT (Reversible Addition-Fragmentation chain Transfer) at 115 ° C for 4.5 hours. The polymerization reaction was carried out. After polymerization, the reaction solution was precipitated in 250 mL of an extraction solvent, and then filtered and dried under reduced pressure to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 23,400 and 1.12, respectively. The block copolymer comprises a first block (volume fraction of the first block: 0.5) derived from the monomer (A) of Preparation Example 1 and a agent derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.5). Contains 2 blocks. The block copolymer (A) exhibits a pitch (L) of about 18.4 nm when the lamellar pattern is formed, and the pitch can be confirmed by the Fast Fourier Transform method for the block copolymer forming the lamellar pattern.

Preparation Example 3 Synthesis of Block Copolymer (B)

5 g of Monomer (A) of Preparation Example 1, 128 mg of cyanoisoprotyldithiobenzoate as a Reversible Addition-Fragmentation Chain Transfer (RAFT) reagent, 9.5 mg of Azobisisobutyronitrile (AIBN) as a radical initiator and 12.0 mL of anisole 25 In a mL Schlenk flask was stirred for 30 minutes at room temperature under a nitrogen atmosphere and then subjected to RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction at 70 ℃ for 4 hours. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the macroinitiator was about 68% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 8,900 and 1.19, respectively. 0.5 g of the macroinitiator, 5.9 g of pentafluorostyrene monomer and 2.1 mL of anisole were added to a 25 mL Schlenk flask, stirred at room temperature for 30 minutes under nitrogen atmosphere, and then RAFT (Reversible Addition-Fragmentation chain Transfer) at 115 ° C. for 4 hours. ) Polymerization reaction was carried out. After polymerization, the reaction solution was precipitated in 250 mL of an extraction solvent, and then filtered and dried under reduced pressure to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 23,300 and 1.14, respectively. The block copolymer comprises a first block (volume fraction of the first block: 0.49) derived from the monomer (A) of Preparation Example 1 and a agent derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.51). Contains 2 blocks. The block copolymer (A) exhibits a pitch (L) of about 19.1 nm when the lamellar pattern is formed.

Preparation Example 4 Synthesis of Block Copolymer (C)

5 g of Monomer (A) of Preparation Example 1, 21.3 mg of cyanoisoprotyldithiobenzoate as a Reversible Addition-Fragmentation Chain Transfer (RAFT) reagent, 15.8 mg of Azobisisobutyronitrile (AIBN) as a radical initiator and 12.2 mL of anisole 25 In a mL Schlenk flask was stirred for 30 minutes at room temperature under a nitrogen atmosphere and then subjected to RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction at 70 ℃ for 4 hours. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the macroinitiator was about 68% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 7,500 and 1.17, respectively. 1 g of the macro initiator, 13.5 g of pentafluorostyrene monomer, and 4.8 mL of anisole were added to a 25 mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then RAFT (Reversible Addition-Fragmentation chain Transfer) at 115 ° C. for 6.5 hours. ) Polymerization reaction was carried out. After polymerization, the reaction solution was precipitated in 250 mL of an extraction solvent, and then filtered and dried under reduced pressure to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 22,300 and 1.14, respectively. The block copolymer comprises a first block (volume fraction of the first block: 0.44) derived from the monomer (A) of Preparation Example 1 and a agent derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.56). Contains 2 blocks. The block copolymer (A) exhibits a pitch (L) of about 18.1 nm when a lamellar pattern is formed.

Preparation Example 5 Synthesis of Random Copolymer (A)

3.8 g of styrene monomer, 0.57 g of glycydyl methacrylate (GMA), 33 mg of AIBN (Azobisisobutyronitrile) and 4.4 g of tetrahydrofuran (THF) were placed in a serum bottle and stirred for 30 minutes at room temperature under a nitrogen atmosphere. Free Radical Polymerization (FRP) reaction was performed at 60 ° C. for about 12 hours. After the polymerization, the reaction solution was precipitated in methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a random copolymer (A). The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the random copolymer were 32,500 and 1.70, respectively.

Example 1.

A stripe pattern was formed on a silicon wafer substrate by using the random copolymer (A) of Preparation Example 5. The polymer stripe pattern on the silicon wafer may be formed by ArF immersion lithography or E-beam lithography (EBL). That is, by forming the polymer lines of the shape as shown in Figure 1 by the ArF immersion lithography or E-beam lithography (EBL) method to form a stripe pattern and crosslinking for 5 minutes at a temperature of about 200 ℃ Can be. The stripe pattern was formed such that polymer lines having a width W of about 25 nm were arranged at a pitch F of about 90 nm. At this time, the thickness of each polymer line was formed to about 10nm. Subsequently, the coating liquid prepared by dissolving the block copolymer (A) of Preparation Example 2 in a concentration of about 1.0% by weight in fluorobenzene was coated on the substrate to a thickness of about 25.6 nm, and at about 230 ° C. for about 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 2 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure with excellent straightness is effectively formed.

Example 2.

A stripe pattern was formed on the silicon wafer substrate in the same manner as in Example 1 using the random copolymer (A) of Preparation Example 5. The stripe pattern is formed such that a plurality of polymer lines having a width W of about 23 nm are arranged at a pitch F of about 90 nm. Subsequently, a coating liquid prepared by dissolving the block copolymer (B) of Preparation Example 3 in a concentration of about 1.0 wt% in fluorobenzene was coated on the substrate to a thickness of about 26.7 nm, and thermally at about 230 ° C. for 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 3 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure excellent in straightness is effectively formed.

Comparative Example 1.

A pinning stripe pattern was formed on the silicon wafer substrate in the same manner as in Example 1 using the random copolymer (A) of Preparation Example 5. The stripe pattern was formed such that a plurality of polymer lines having a width W of about 12 nm were arranged at a pitch F of about 93 nm. Subsequently, a coating liquid prepared by dissolving the block copolymer (B) of Preparation Example 3 in a concentration of about 1.0 wt% in fluorobenzene was coated on the substrate to a thickness of about 26.7 nm, and thermally at about 230 ° C. for 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 4 is a result of the self-assembled block copolymer film, it can be seen from the figure that the linearity of the self-assembly structure is not secured.

Comparative Example 2.

A pinning stripe pattern was formed on the silicon wafer substrate in the same manner as in Example 1 using the random copolymer (A) of Preparation Example 5. The stripe pattern was formed such that a plurality of polymer lines having a width W of about 9 nm were arranged at a pitch F of about 90 nm. Subsequently, a coating liquid prepared by dissolving the block copolymer (C) of Preparation Example 4 in a concentration of about 1.0 wt% in fluorobenzene was coated on the substrate to a thickness of about 26.3 nm, and thermally at about 230 ° C. for 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 5 is a result of the self-assembled block copolymer film, it can be seen from the figure that the efficiency of securing the straightness of the self-assembly structure is inferior.

Comparative Example 3.

A pinning stripe pattern was formed on the silicon wafer substrate in the same manner as in Example 1 using the random copolymer (A) of Preparation Example 5. The stripe pattern was formed such that a plurality of polymer lines having a width W of about 15 nm were arranged at a pitch F of about 84 nm. Subsequently, a coating liquid prepared by dissolving the block copolymer (B) of Preparation Example 3 in a concentration of about 1.0 wt% in fluorobenzene was coated on the substrate to a thickness of about 26.7 nm, and thermally at about 230 ° C. for 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 6 is a result of the self-assembled block copolymer film, it can be seen from the figure that the efficiency of securing the straightness of the self-assembly structure is inferior.

Comparative Example 4.

A pinning stripe pattern was formed on the silicon wafer substrate in the same manner as in Example 1 using the random copolymer (A) of Preparation Example 5. The stripe pattern was formed such that a plurality of polymer lines having a width W of about 15 nm were arranged at a pitch F of about 112 nm. Subsequently, a coating liquid prepared by dissolving the block copolymer (B) of Preparation Example 3 in a concentration of about 1.0 wt% in fluorobenzene was coated on the substrate to a thickness of about 26.7 nm, and thermally at about 230 ° C. for 5 minutes. Thermal annealing formed a film comprising the self-assembled block copolymer. 7 is a result of the self-assembled block copolymer film, it can be seen from the figure that the efficiency of ensuring the straightness of the self-assembly structure is inferior.

Claims (10)

Forming a lamellar pattern of the block copolymer on a substrate having a stripe pattern formed of a plurality of polymer lines,
The ratio (F / L) of the pitch (F) between the plurality of polymer lines and the pitch (L) of the lamellar pattern of the block copolymer is in the range of 4.5 to 5.5, and the width (W) of the polymer line and the block The ratio (W / L) of the pitch (L) of the lamellar pattern of the copolymer is 1 or more, and the spacing (FW) between adjacent polymer lines among the plurality of polymer lines and the pitch (L) of the lamellar pattern of the block copolymer. Ratio ((FW) / L) is 4 or less, and the block copolymer has a first block including a unit represented by the following Chemical Formula 1 and a second block including a unit represented by the following Chemical Formula 2 :
[Formula 1]

In formula (1), R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, Z is a hydrocarbon chain of 8 to 20 carbon atoms:
[Formula 2]

In Formula 2, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms including three or more halogen atoms. The method of claim 1, wherein the surface on which the stripe pattern of the substrate does not exist is a bare surface, and the lamella pattern of the block copolymer is formed by contacting the stripe pattern and the bare surface. The method of claim 1, wherein the width of the polymer line is in the range of 15 to 30 nm. The method of manufacturing a patterned substrate according to claim 1, wherein the pitch between the polymer lines is in the range of 80 to 100 nm. The method of claim 1, wherein the polymer lines are each polystyrene lines. The method of claim 1, wherein the polymer lines are each crosslinked polystyrene lines. The method of claim 1, wherein the pitch of the lamellar patterns of the block copolymer is in the range of 15 to 25 nm. The method of claim 1, wherein the block copolymer has a number average molecular weight in the range of 10,000 to 30,000. The method of claim 1, further comprising selectively removing any of the first and second blocks of the block copolymer. The method of claim 9, further comprising selectively removing any one of the first and second blocks, and etching the substrate using the remaining block copolymer pattern as a mask.

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