KR102248924B1 - Method for forming pattern and laminate - Google Patents

Abstract

The present application provides a pattern forming method and a laminate capable of preventing structural collapse or shape defects while providing etching selectivity in etching a block copolymer forming a self-assembled structure.

Description

Pattern formation method and laminated body {METHOD FOR FORMING PATTERN AND LAMINATE}

The present application relates to a pattern forming method and a laminate.

Block copolymers in which two or more chemically distinct polymer chains are connected by covalent bonds can be separated into regular microphases due to their self-assembly characteristics. The microphase separation phenomenon of these block copolymers is generally explained by the volume fraction, molecular weight, and the Flory-Huggins interaction parameter between the constituents, and nanoscale spheres, cylinders, and gyroids. (gyroid) or lamella (lamella), etc. can form a variety of structures.

In general, the orientation of the nanostructures in the block copolymer film may be determined by whether any one of the blocks of the block copolymer is exposed to the surface or air. That is, the orientation of the nanostructures can be determined by selective wetting of the corresponding block. In general, since a number of substrates are polar and air is non-polar, blocks having a larger polarity in the block copolymer are wetted onto the substrate. Blocks with a smaller polarity are wetting at the interface with air, leading to a parallel orientation.

In order to apply the self-assembled structure of the block copolymer to nanolithography, a process of selectively removing the polymer of one block through various etching processes is required. However, etching selectivity varies depending on the type and composition of the block copolymer to be etched, and selective etching may be difficult in some cases. In addition, there is a problem in that structural collapse or defects occur depending on the shape and line width of the copolymer block, the type of substrate, and the like.

The present application provides a pattern forming method and a laminate capable of preventing structural collapse or shape defects while providing etching selectivity in etching a block copolymer forming a self-assembled structure.

In the present specification,'and/or' is used to mean including at least one or more of the elements listed before and after.

In the present specification, the term monovalent or divalent hydrocarbon group may mean a monovalent or divalent residue derived from a compound consisting of carbon and hydrogen or a derivative thereof, unless otherwise specified. In the above, examples of the compound consisting of carbon and hydrogen include alkanes, alkenes, alkynes, or aromatic hydrocarbons.

In the present specification, 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 with one or more substituents.

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

In the present specification, the term alkenyl group or alkynyl group refers to 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.

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

In the present specification, 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. It can mean qi. The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the term aryl group or arylene group, unless otherwise specified, one benzene ring structure, two or more benzene rings are linked while sharing one or two carbon atoms, or linked by an arbitrary linker It may mean a monovalent or divalent moiety derived from a compound or a derivative thereof having a structure to be formed.

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.

In the present application, the term aromatic structure may mean the aryl group or an arylene group.

In the present specification, 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 mean a case where no separate atom exists at the corresponding site. For example, in the case where B is a single bond in the structure indicated by A-B-C, it may mean that no separate atom exists at the site indicated by B, and A and C are directly connected to form a structure indicated by A-C.

In the present application, substituents that may be optionally substituted in an alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group, alkoxy group, aryl group, arylene group, straight chain or aromatic structure, etc., include hydroxy group, halogen Atom, carboxyl group, glycidyl group, acryloyl group, methacryloyl group, acryloyl group oxy, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynyl A ren group, an alkoxy group, or an aryl group may be exemplified, but is not limited thereto.

In the present application, the term pattern may refer to a shape formed on the surface of a film including the block copolymer due to the self-assembled structure of the block copolymer, and may refer to a pattern including two or more lines.

The present application relates to a method of forming a pattern. The pattern formation method of the present application is an atomic layer deposition (ALD) on the polymer film of a substrate on which a self-assembled polymer film comprising a polymer segment A and a block copolymer having a polymer segment B different from the segment A is formed. It may include forming a metal-containing layer by using. By forming a metal-containing layer on the polymer film, it is possible to improve the etching resistance of the film containing the block copolymer, thereby preventing collapse of the structure during etching.

The atomic layer deposition (ALD) uses a vapor phase chemical vapor deposition reaction, but by injecting a precursor and a reactant in time division to suppress the vapor phase reaction and self-controlling reaction on the surface of the substrate (Self- Limited reaction) may mean a process technology of accurately controlling the thickness of a thin film to deposit. Atomic layer deposition proceeds in a cycle manner, and generally, one growth cycle consists of four steps: ① precursor supply ② purge ③ reactant supply ④ purge. These four steps are a basic cycle for thin film growth, and the cycle of atomic layer deposition technology in thin film formation is repeated for the required thickness deposition. Therefore, the atomic layer deposition technology can accurately control the thickness of the thin film according to the number of cycles.

In one example of the present application, the metal-containing layer formed by atomic layer deposition may be formed substantially only on the polymer segment A of the block copolymer, or may be formed only on the polymer segment B. That the metal-containing layer is substantially formed only on one segment of the block copolymer, for example, the metal-containing layer is formed in an area ratio of 90% or more on any one of the polymer segment A and the polymer segment B, and the other segment It may mean that the metal-containing layer is formed in an area ratio of 10% or less on the top. For example, when the metal-containing layer is substantially formed only on the polymer segment A, the metal-containing layer on the polymer segment A is 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96 % Or more, 97% or more, 98% or more, 99% or more, or 100% may be formed, but is not limited thereto. In addition, in the above case, the metal-containing layer on the polymer segment B is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less. Alternatively, it may be formed in 0%, but is not limited thereto. In addition, when the metal-containing layer is substantially formed only on the polymer segment B, the metal-containing layer is 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% on the polymer segment B. Above, 97% or more, 98% or more, 99% or more, or 100% may be formed, but is not limited thereto. In addition, in the above case, the metal-containing layer on the polymer segment A is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less. Alternatively, it may be formed in 0%, but is not limited thereto. As described above, by allowing the metal-containing layer to be formed only on the polymer segment A or only on the polymer segment B, a metal-containing layer can be selectively formed on a specific block of the block copolymer, and is formed in a self-assembled structure of the block copolymer. A metal-containing layer may be selectively formed on the pattern. Through this, etching selectivity for the self-assembled structure of the block copolymer may be secured, and in particular, even when the polymer segment A and the polymer segment B included in the block copolymer share a specific chemical structure, the etching selectivity may be exhibited.

In one example, the polymer segment A of the block copolymer according to the present application may include a unit represented by Formula 1 below.

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group, X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, -C(=O) -X ₁ -or -X ₁ -C(=O)-, wherein X ₁ is an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and Y Is a monovalent substituent including a ring structure to which a chain having 8 or more chain forming atoms is connected.

In Formula 1, X may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O-, or -OC(=O)-, or -C(=O)-O-, in another example, It is not limited.

In Formula 1, the monovalent substituent of Y includes a chain structure formed of at least 8 chain-forming atoms.

In the present application, the term chain-forming atom refers to an atom that forms a linear structure of a predetermined chain. The chain may be linear or branched, but the number of chain-forming atoms is calculated only from the number of atoms forming the longest straight chain, and other atoms bonded to the chain-forming atom (e.g., chain-forming atoms In the case of a carbon atom, the hydrogen atom bonded to the carbon atom, etc.) is not counted. In addition, 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. For example, when the chain is an n-pentyl group, all of the chain-forming atoms are carbon and the number is 5, and even when the chain is a 2-methylpentyl group, all of the chain-forming atoms are carbon and the number is 5. As the chain-forming atom, carbon, oxygen, sulfur, or nitrogen may be exemplified, 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 chain-forming atoms may also be 30 or less, 25 or less, 20 or less, or 16 or less.

The unit of Formula 1 may allow the block copolymer to exhibit excellent self-assembly properties.

In one example, the chain may be a straight-chain hydrocarbon chain such as a straight-chain alkyl group. In this case, the alkyl group may be an alkyl group having 8 or more carbon atoms, 8 to 30 carbon atoms, 8 to 25 carbon atoms, 8 to 20 carbon atoms, or 8 to 16 carbon atoms. At least one of the carbon atoms of the alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted with another substituent.

In Formula 1, Y includes a ring structure, and the chain may be connected to the ring structure. By such a ring structure, the self-assembly property of the block copolymer formed by the monomer may be further improved. The ring structure may be an aromatic structure or an alicyclic structure.

The chain may be directly connected to the ring structure or may be connected via a linker. As the linker, an oxygen atom, a sulfur atom, -NR ₁ -, S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, -C(=O)-X ₁ -or- X ₁ -C(=O)- and the like may be exemplified, wherein R ₁ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and X ₁ is a single bond, an oxygen atom, a sulfur atom , -NR ₂ -, -S(=O) ₂ -, may be an alkylene group, an alkenylene group or an alkynylene group, wherein R ₂ may be a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group have. An oxygen atom or a nitrogen atom may be exemplified as a suitable linker. The chain may be connected to an aromatic structure via, for example, an oxygen atom or a nitrogen atom. In this case, the linker may be an oxygen atom, or -NR _1- (wherein R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

Y in Formula 1 may be represented by the following Formula 2 in an example.

[Formula 2]

In Formula 2, P is an arylene group, Q is a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is 8 It is the chain having more than one chain forming atom. When Y in Formula 1 is a substituent of Formula 2, P in Formula 2 may be directly connected to X in Formula 1.

As a suitable example of P in Formula 2, an arylene group having 6 to 12 carbon atoms, for example, a phenylene group may be exemplified, but is not limited thereto.

In Formula 2, Q is a suitable example, an oxygen atom or -NR _1- (wherein R ₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

As a suitable example of the unit of Formula 1, in Formula 1, R is hydrogen or an alkyl group, for example, hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, and Y is the above In Formula 2, P is an arylene group or phenylene having 6 to 12 carbon atoms, Q is an oxygen atom, and Z is a unit of the aforementioned chain having 8 or more chain forming atoms.

Accordingly, examples of suitable units of Formula 1 include units of Formula 3 below.

[Formula 3]

In Formula 3, 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, and Z is a chain forming valency. It is the above chain of 8 or more.

The block copolymer of the present application may include units represented by Formula 1, Formula 2 and/or Formula 3 to exhibit excellent self-assembly characteristics of the block copolymer, and the self-assembled structure of the block copolymer is vertically aligned. Lamella structure can be formed.

In one example, the metal-containing layer of the present application may be formed at 125°C or higher. The formation temperature of the metal-containing layer is 127°C or higher, 129°C or higher, 130°C or higher, 131°C or higher, 133°C or higher, 135°C or higher, 137°C or higher, 139°C or higher, 141°C or higher, 143°C or higher, and 145°C. It may be above, 147°C or higher, 148°C or higher, or 150°C or higher. The upper limit of the temperature is not particularly limited as long as it is less than or equal to the thermal decomposition temperature of the precursor or the structural transformation temperature (Order-Disorder Transition, ODT) of the block copolymer, and may vary depending on the type of the precursor or block copolymer to be used. The upper limit of the temperature may be, for example, 350°C or less or 300°C or less, but is not limited thereto.

The formation temperature of the metal-containing layer may be a temperature in the step of supplying a reactant during the growth cycle of the atomic layer deposition described above. In the reactant supply step, the metal-containing layer may be grown through a reduction reaction of the metal compound of the precursor forming the metal-containing layer, and when the formation temperature of the metal-containing layer satisfies the above range, the metal-containing layer is formed only on the polymer segment A, or Alternatively, it can be made to be formed only in the polymer segment B. The temperature range may be the same in the step of ① precursor supply, ② purge and/or ④ purge during the growth cycle of atomic layer deposition.

In an example of the present application, by applying the ALD process in the above temperature range on a film formed from a block copolymer in which the polymer segment A includes the unit represented by Formula 1, substantially forming a metal-containing layer only on the polymer segment A. Can be controlled. In this case, the metal-containing layer on the polymer segment A is 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, 99% or more Alternatively, it may be 100% formed, and the metal-containing layer on the polymer segment B is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% Hereinafter, 1% or less or 0% may be formed, but is not limited thereto.

In another example of the present application, the metal-containing layer formed by atomic layer deposition may be incorporated in the polymer film. Incorporation of the metal-containing layer into the polymer film may mean a state in which the precursor for forming the metal-containing layer penetrates into the polymer film and then the metal-containing layer is formed, so that a part of the polymer film is deformed to include the metal-containing layer. Therefore, as described above, when the metal-containing layer is formed only on the polymer segment A, the metal-containing layer is formed on the polymer segment A, and the metal-containing layer is mixed in the polymer segment A, so that a part of the polymer segment A may be deformed. In addition, when the metal-containing layer is formed only in the polymer segment B, the metal-containing layer is formed on the polymer segment B, and the metal-containing layer is mixed in the polymer segment B, so that a part of the polymer segment B may be deformed. When the metal-containing layer is mixed with all of the polymer segment A or the polymer segment B, all of the polymer segment A or the polymer segment B may be deformed. The method of modifying a part of the polymer film by incorporating the metal-containing layer into the polymer film is not particularly limited as long as it is capable of forming a metal-containing layer on the polymer film and modifying a part of the polymer film.For example, Sequential Infiltration Synthesis , SIS) method can be used.

In an example of the present application, the precursor for forming the metal-containing layer may exhibit affinity with a compound included in the polymer segment A or the polymer segment B of the block copolymer. The meaning that the precursor has an affinity with the compound contained in the polymer segment means that the precursor and the polymer segment are physically and/or chemically due to physical and/or chemical properties between the metal compound contained in the precursor and the compound contained in the polymer segment. It could mean that there is a force to form bonds, bonds, and contacts. The force due to physical and/or chemical properties between the metal compound included in the precursor and the compound included in the polymer segment is not particularly limited as long as the force exists between the metal compound of the precursor and the compound included in the polymer segment, For example, it may be a permanent dipole-permanent dipole force, a permanent dipole-induced dipole force, an induced dipole-induced dipole force, a force due to hydrogen bonding or a force due to ionic bonding. In addition, affinity for different components is a relative concept, and it can be expressed that a component having a higher affinity has an affinity compared to other components. When the precursor has an affinity with the compound contained in the polymer segment A, the metal-containing layer may be formed only on the polymer segment A of the block copolymer, and if the precursor has an affinity with the compound contained in the polymer segment B, the metal The containing layer can be formed only on the polymer segment B of the block copolymer. For example, if the affinity between the precursor and the polymer segment A is greater than the affinity between the precursor and the polymer segment B, the metal-containing layer may be formed only on the polymer segment A, and the affinity between the precursor and the polymer segment B is the precursor and the polymer segment A. If it is greater than the affinity of the liver, the metal-containing layer can only be formed on the polymer segment B. As described above, by having an affinity between the precursor and the compound contained in the polymer segment, the precursor may be adsorbed only to the polymer segment A or only to the polymer segment B in the step ① of the precursor supply during the growth cycle of the atomic layer deposition.

The precursor forming the metal-containing layer of the present application is at least one selected from the group consisting of (organic) metal compounds, (organic) metal complexes, (organic) metal clusters, metal nanoparticles, metal particles or fragments, and combinations thereof. It may include. The precursor is, for example, an organometallic compound, the precursor is aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, rhodium, iridium, nickel, At least one metal compound selected from the group consisting of metal compounds such as palladium, platinum, copper, silver, gold, zinc, cadmium, gallium, indium, thallium, tin, lead, and bismuth, clusters of metal compounds, and particles of metal compounds It may include, but is not limited thereto. The type of the precursor may vary depending on the type of the block copolymer to form the metal-containing layer, and for example, trimethylaluminum (TMA), diethylzinc (DEZ), or the like may be used.

The pattern formation method of the present application may further include a step of selectively removing any one polymer segment of the block copolymer forming the self-assembled structure after forming the metal-containing layer. In the above method, a method of selectively removing any one block of the block copolymer is not particularly limited, and for example, a method of removing relatively soft blocks by irradiating an appropriate electromagnetic wave, for example, ultraviolet rays, etc., to the polymer membrane is employed. Alternatively, methods such as Inductively Coupled Plasma Etching or Reactive Ion Etching (RIE) may be used.For example, a polymer segment of the block copolymer may be selectively selected through reactive ion etching. Can be removed. The reactive ion etching may be performed according to a known method, and the etching conditions are not particularly limited, and, for example, argon or oxygen may be used as a reactive gas.

The method of forming a pattern of the present application may further include etching the substrate using a polymer layer from which one of the polymer segments has been removed as a mask. The step of etching the substrate using the polymer film from which the polymer segment has been selectively removed as a mask is not particularly limited, and for example, it can be performed through a reactive ion etching step using _{CF 4 /Ar ions, etc., following this process.} A step of removing the polymer film from the substrate by oxygen plasma treatment or the like and a step of removing the metal-containing layer using reactive ion etching or the like may also be performed.

The block copolymer of the present application may implement a periodic structure including a sphere, a cylinder, a gyroid, or a lamellar through self-assembly. Among the structures, in the case of spheres or lamellas, the block copolymer may exist in a vertically oriented state.

In one example, the polymer segment B of the block copolymer of the present application may include a unit represented by Formula 4 below.

[Formula 4]

In Formula 4, X ₂ 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, an alkenylene group, or an alkynylene group, and W is at least one halogen It is an aryl group containing an atom. In the above, W may be an aryl group substituted with at least one halogen atom, for example, an aryl group having 6 to 12 carbon atoms substituted with 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms.

In addition, the polymer segment B included in the block copolymer may include a unit represented by Formula 5 below.

[Formula 5]

In Formula 5, X ₂ 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, an alkenylene group, or an alkynylene group, and 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 contained in _{R 1} to R _{5 is 1 or more.}

In Chemical Formula 5, X ₂ may be a single bond, an oxygen atom, an alkylene group, -C(=O)-O- or -OC(=O)- in another example.

In Formula 5, R ₁ to R ₅ are each independently hydrogen, an alkyl group, a haloalkyl group, or a halogen atom, but R ₁ to R ₅ are 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms , For example, it may contain a fluorine atom. The _{halogen atoms contained in R 1} to R ₅ , for example, fluorine atoms may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The block copolymer according to the present application may include the units of Formula 4 or 5 so that the block copolymer exhibits excellent self-assembly characteristics.

The present application also relates to a laminate. The laminate of the present application includes a substrate; A self-assembled polymer film formed on the substrate and comprising a block copolymer including a polymer segment A and a polymer segment B different from the segment A; And a metal-containing layer, and the metal-containing layer may be formed only on the polymer segment A or the polymer segment B. The polymer segment A may include a unit represented by Formula 1, and the polymer segment B may include a unit represented by Formula 4 above. In addition, the self-assembled structure of the block copolymer may be a cylinder, sphere, or lamellar structure. Detailed descriptions of the block copolymer, polymer segments A and B, and the metal-containing layer included in the laminate of the present application are the same as described in the above-described pattern formation method, and thus will be omitted.

In the present application, a specific method of preparing the block copolymer as described above is not particularly limited as long as it includes the polymer segment A and/or the polymer segment B described above.

For example, the block copolymer can be prepared by using the monomer LRP (Living Radical Polymerization) method. For example, anionic polymerization synthesized in the presence of inorganic acid salts such as alkali metals or alkaline earth metal salts by using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator, polymerization of an organic alkali metal compound Anionic polymerization method that is used as an initiator and synthesized in the presence of an organic aluminum compound, atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization control agent, and an atom transfer radical polymerization agent as a polymerization control agent. ARGET (Activators Regenerated by Electron Transfer) atom transfer radical polymerization (ATRP), ICAR (Initiators for continuous activator regeneration) atom transfer radical polymerization (ATRP), reversible addition of inorganic reducing agents- There are reversible addition-cleavage chain transfer polymerization method (RAFT) using a cleavage chain transfer agent or a method using an organic tellurium compound as an initiator, and a suitable method may be selected and applied from among these methods.

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

When preparing a block copolymer, a method of forming another block included in the copolymer together with a block formed using the monomer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired block. Blocks can be formed.

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

The kind of radical initiator is not particularly limited, and may be appropriately selected in consideration of polymerization efficiency, for example, AIBN (azobisisobutyronitrile), ABCN (1,1'-Azobis (cyclohexanecarbonitrile)) or 2,2'-azobis- Azo compounds such as 2,4-dimethylvaleronitrile (2,2'-azobis-(2,4-dimethylvaleronitrile)) or peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP) are used. Can be used.

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

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

The present application provides a pattern forming method and a laminate capable of preventing structural collapse or shape defects while providing etching selectivity in etching a block copolymer forming a self-assembled structure.

1 is an SEM image showing the results of Example 1 in which alumina was formed only in polymer segment A.
2 is a SEM image after removing the polymer segment B in Example 1.
3 is a SEM image after removing the polymer segment B in Example 2. FIG.
4 is an SEM image after removing the polymer segment B in Example 3. FIG.
5 and 6 are SEM images of the results of Comparative Example 1.
7 is an SEM image of the result of Comparative Example 2.

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

Preparation Example 1. Synthesis of Monomer (A)

The compound of the following formula A (DPM-C12) was synthesized in the following manner. Hydroquinone (10.0g, 94.2 mmol) and 1-Bromododecane (23.5 g, 94.2 mmol) were added to a 250 mL flask, dissolved in 100 mL of acetonitrile, and then an excess of Potassium carbonate was added and reacted at 75° C. for about 48 hours under nitrogen conditions. Potassium carbonate remaining after the reaction was removed by filtering, and acetonitrile used in the reaction was also removed. A mixed solvent of DCM (dichloromethane) and water was added thereto to work up, and the separated organic layer was collected and passed through _{MgSO 4 to dehydrate.} Subsequently, in column chromatography, using DCM (dichloromethane) to obtain the target product (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as a white solid in a yield of about 37%.

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

[Formula A]

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

Preparation Example 2. Synthesis of Block Copolymer (A-1)

2.0 g of the monomer (A) of Preparation Example 1 and 64 mg of cyanoisopropyldithiobenzoate as a Reversible Addition Fragmentation Chain Transfer (RAFT) reagent, 23 mg of AIBN (Azobisisobutyronitrile) as a radical initiator, and 5.34 mL of benzene were added to a 10 mL Schlenk flask. The mixture was placed in a nitrogen atmosphere and stirred at room temperature for 30 minutes, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 70° C. for 4 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the giant initiator 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 added to a 10 mL Schlenk flask, stirred at room temperature under a nitrogen atmosphere for 30 minutes, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction at 115° C. for 4 hours Was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink block copolymer. The block copolymer is derived from the monomer (A) of Preparation Example 1 and includes a polymer segment A having 12 chain forming atoms (the number of carbon atoms in R in Chemical Formula A) and a polymer segment B derived from the pentafluorostyrene monomer. .

Preparation Example 3. Synthesis of Block Copolymer (A-2)

2.0 g of the monomer (A) of Preparation Example 1, 42.6 mg of cyanoisopropyldithiobenzoate as a Reversible Addition Fragmentation Chain Transfer (RAFT) reagent, 3.2 mg of AIBN (Azobisisobutyronitrile) as a radical initiator, and 4.77 g of anisol were added to 10 mL Schlenk. After placing in a flask and stirring at room temperature for 30 minutes under a nitrogen atmosphere, RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction was performed at 70° C. for 4 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the giant initiator was about 73.3% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 7,500 and 1.17, respectively. 0.3 g of macroinitiator, 2.24 g of pentafluorostyrene monomer, and 1.306 mL of benzene were added to a 10 mL Schlenk flask, stirred at room temperature under nitrogen atmosphere for 30 minutes, and then RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction at 115° C. for 6 hours Was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink block copolymer. The block copolymer is derived from the monomer (A) of Preparation Example 1 and includes a polymer segment A having 12 chain forming atoms (the number of carbon atoms in R in Chemical Formula A) and a polymer segment B derived from the pentafluorostyrene monomer. .

A compound of formula A (DPM-C12) and a pentafluorostyrene random copolymer were coated on a silicon substrate and fixed to a silicon wafer through a thermal annealing process at 160°C for 24 hours, and unreacted substances were removed. To do this, a sonication process was performed on a fluorobenzene solution for 10 minutes. The lamellar pattern formed by coating the block copolymer (A-1) on the above substrate and thermally annealing at 160° C. for 1 hour was confirmed through SEM. The pitch of the formed lamella pattern was confirmed to be 29 nm.

TMA (trimethylaluminum) was injected into the block copolymer having the vertically oriented lamellar structure for 120 seconds, and purged under a nitrogen atmosphere. Purging was carried out at a flow rate of 50 sccm for 600 seconds at a pressure of 1.6 Torr. After purging, water was added for 120 seconds, and then purged under the same conditions under a nitrogen atmosphere, and the entire process was carried out at 150°C. After repeating the cycle 10 times, the result of forming alumina in the block copolymer was confirmed through SEM. 1 shows a result of forming alumina only in the polymer segment A as a result of Example 1 above.

The polymer segment B of the block copolymer in which alumina was formed only in the polymer segment A was removed through reactive ion etching (RIE). 2 is an SEM image after removing the polymer segment B.

As shown in FIG. 2, alumina penetrated into the structure of the polymer segment A to show etching resistance, and a structure in which alumina was mixed even after etching was confirmed.

Example 2

A lamellar pattern formed by coating a block copolymer (A-2) on an untreated silicon substrate and thermally annealing at 160° C. for 1 hour was confirmed through SEM. The pitch of the formed lamella pattern was confirmed to be 15.6nm. The block copolymer (A-2) used at this time has a characteristic of being vertically oriented on an untreated substrate and horizontally oriented on a substrate on which a composition for forming a guide pattern is formed. As a result of observation through SEM, a vertically oriented lamellar structure Was observed.

TMA (trimethylaluminum) was injected into the block copolymer having the vertically oriented lamellar structure for 120 seconds, and purged under a nitrogen atmosphere. Purging was performed at a flow rate of 50 sccm for 600 seconds at a pressure of 1.6 Torr. After purging, water was added for 120 seconds, and then purged under the same conditions under a nitrogen atmosphere, and the entire process was carried out at 150°C. After repeating the cycle 10 times, the result of forming alumina in the block copolymer was confirmed through SEM. The polymer segment B of the block copolymer in which alumina was formed only in the polymer segment A was removed through reactive ion etching (RIE). 3 is a SEM image after removing the polymer segment B.

As shown in FIG. 3, alumina penetrated into the structure of the polymer segment A to show etching resistance, and a structure in which alumina was mixed even after etching was confirmed.

Example 3

The trench substrate was prepared in the following manner. A silicon wafer was applied as a substrate. A layer of SiO was formed on the substrate to a thickness of about 200 nm by a known deposition method. Subsequently, a BARC (bottom anti reflective coating) was coated on the SiO layer to a thickness of about 60 nm, and a PR (photoresist, KrF, positive-tone resist) layer was coated on the top of the SiO layer to a thickness of about 400 nm. . Subsequently, the PR layer was patterned using a KrF stepper exposure method. Subsequently, using the patterned PR layer as a mask using the RIE (re active ion etching) method as a mask, the BARC layer and the SiO layer thereunder were etched, and the residue was removed to form a trench structure.

A compound (DPM-C12) and a pentafluorostyrene random copolymer were coated inside the trench and fixed on a silicon wafer through a thermal annealing process at 160°C for 24 hours. The sonication process was performed for 10 minutes on a fluorobenzene solution. A lamellar pattern formed by coating a block copolymer (A-1) inside the trench and thermally annealing at 200° C. for 1 hour was confirmed through SEM.

TMA (trimethylaluminum) was injected into the block copolymer having the vertically oriented lamellar structure for 120 seconds, and purged under a nitrogen atmosphere. Purging was performed at a flow rate of 50 sccm for 600 seconds at a pressure of 1.6 Torr. After purging, water was added for 120 seconds, and then purged under the same conditions under a nitrogen atmosphere, and the entire process was carried out at 150°C. After repeating the cycle 10 times, the result of forming alumina in the block copolymer was confirmed through SEM. The polymer segment B of the block copolymer in which alumina was formed only in the polymer segment A was removed through reactive ion etching (RIE). 4 is an SEM image after removing the polymer segment B.

As shown in FIG. 4, alumina penetrated into the structure of the polymer segment A to show etching resistance, and a structure in which alumina was mixed even after etching was confirmed.

Comparative Example 1

The experiment was performed under the same conditions as in Example 1, except that the atomic layer deposition (ALD) process was performed at 120°C.

5 is an SEM image showing the result of Comparative Example 1, and as a result of the experiment, it was confirmed that alumina was formed in both the polymer segment A and the polymer segment B.

6 is an SEM image showing the results of reactive ion etching on a substrate having alumina formed on both the polymer segment A and the polymer segment B. As shown in FIG. 4, it was confirmed that the etching selectivity was deteriorated and a defect occurred in the structure after etching.

Comparative Example 2

The experiment was performed under the same conditions as in Example 2, except that the atomic layer deposition (ALD) process was performed at 120°C.

FIG. 7 is an SEM image showing the result of Comparative Example 2, and is an SEM image showing the result of reactive ion etching on a substrate having alumina formed on both the polymer segment A and the polymer segment B. As shown in FIG. 7, it was confirmed that the etching selectivity was lowered and a defect occurred in the structure after etching.

Claims (17)

A metal-containing layer is formed on the polymer film of a substrate on which a self-assembled polymer film including a polymer segment A and a block copolymer having a polymer segment B different from the segment A is formed using ALD Including the step of,
The metal-containing layer is formed in an area ratio of 90% or more on the polymer segment A of the self-assembled polymer film, and is formed in an area ratio of 10% or less on the polymer segment B,
The polymer segment A includes a unit represented by Formula 3 below, and the polymer segment B includes a unit represented by Formula 4 below:
[Formula 3]

[Formula 4]

In Formula 3, 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, and Z is 8 or more It is a monovalent substituent including a ring structure in which a chain having a chain-forming atom is connected.
In Formula 4, X ₂ 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, an alkenylene group, or an alkynylene group, and W is at least one halogen It is an aryl group containing an atom.
delete The method of claim 1, wherein the ALD process is performed at 130°C or higher.
delete The method of claim 1, wherein the metal-containing layer is incorporated in the polymer film,
The method of claim 1, wherein the precursor forming the metal-containing layer is an organometallic compound, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, rhodium, 1 selected from the group consisting of metal compounds such as iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, gallium, indium, thallium, tin, lead, and bismuth, clusters of metal compounds, and particles of metal compounds A method for forming a pattern containing more than one kind of metal compound.
The method of claim 1, further comprising the step of selectively removing any one polymer segment of the block copolymer forming the self-assembled structure after forming the metal-containing layer.
8. The method of claim 7, wherein the step of removing any one of the polymer segments uses reactive ion etching.
The method of claim 8, wherein the reactive ion etching is performed using argon or oxygen.
The method of claim 7, further comprising etching the substrate using a polymer layer from which one of the polymer segments has been removed as a mask.
The method of claim 1, wherein the self-assembled structure of the block copolymer is a cylinder, sphere, or lamella structure.
delete Board; A self-assembled polymer film formed on the substrate and comprising a block copolymer including a polymer segment A and a polymer segment B different from the segment A; And a metal-containing layer,
The metal-containing layer is formed in an area ratio of 90% or more on the polymer segment A of the self-assembled polymer film, and is formed in an area ratio of 10% or less on the polymer segment B,
The polymer segment A includes a unit represented by the following formula (3), and the polymer segment B includes a unit represented by the following formula (4):
[Formula 3]

[Formula 4]

In Formula 3, 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, and Z is 8 or more It is a monovalent substituent including a ring structure in which a chain having a chain-forming atom is connected.
In Formula 4, X ₂ 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, an alkenylene group, or an alkynylene group, and W is at least one halogen It is an aryl group containing an atom.
delete delete The laminate according to claim 13, wherein the self-assembled structure of the block copolymer is a cylinder, sphere, or lamellar structure.
The method of claim 13, wherein the metal compound is aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, A laminate of at least one selected from the group consisting of metal compounds such as copper, silver, gold, zinc, cadmium, gallium, indium, thallium, tin, lead, and bismuth, clusters of metal compounds, and particles of metal compounds.

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