KR20190008026A - Method for forming pattern and laminate - Google Patents

Abstract

The present application provides a method of forming a pattern capable of imparting etching selectivity in etching a block copolymer forming a self-assembled structure, and preventing structure collapse or shape imperfection from occurring; and a laminate. The method of forming the pattern includes a step of forming a metal-containing layer by using atomic layer deposition (ALD) on a polymer film of a substrate on which a self-assembled polymer film, including a block copolymer having a polymer segment A and a polymer segment B different from the segment A, is formed.

Description

METHOD FOR FORMING PATTERN AND LAMINATE [0002]

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

Block copolymers in which two or more chemically distinct polymer chains are linked by covalent bonds can be separated into regular microphases due to their self assembly properties. The fine phase separation phenomenon of such a block copolymer is generally explained by the volume fraction, the molecular weight and the mutual attraction coefficient (Flory-Huggins interaction parameter) between the constituent components, and the nanoscale spheres, cylinders, gyroid, lamella, and the like.

Typically, the orientation of the nanostructures in the film of the block copolymer can be determined by whether one of the blocks of the block copolymer is exposed to the surface or air. That is, the orientation of the nanostructure can be determined by selective wetting of the block. Since a plurality of substrates are generally polar and air is non-polar, a block having a larger polarity in a block copolymer is not wetted and the block with smaller polarity is wetted at the interface with air, leading to a parallel orientation.

In order to apply the self-assembled structure of the block copolymer to nanolithography, it is necessary to selectively remove the polymer of one block through various etching processes. However, the etching selectivity varies depending on the type and constituent components of the block copolymer to be etched, and selective etching may be difficult depending on the case. In addition, there is a problem that the structure is collapsed or defective depending on the shape, the line width, the kind of the substrate, and the like of the copolymer block.

The present application provides a pattern forming method and a laminate capable of preventing breakdown of structures and defects in shape while imparting etching selectivity to etching a block copolymer forming a self-assembled structure.

In this specification, 'and / or' are used to mean at least one of the elements listed before and after.

As used herein, the term monovalent or divalent hydrocarbon group may mean a monovalent or divalent moiety derived from a compound or derivative of carbon and hydrogen, unless otherwise specified. Examples of the compound composed of carbon and hydrogen in the above include alkane, alkene, alkyne or aromatic hydrocarbon.

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

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

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

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

As used herein, the term alkenylene group or alkynylene group means an alkenylene group or an alkynylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, It can mean a group. The alkenylene or alkynylene group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

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

The aryl group or the arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms unless otherwise specified.

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

As used herein, the term alicyclic ring structure means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms unless otherwise specified .

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

Examples of the substituent which may optionally be substituted in the present application include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, a linear chain or an aromatic structure, An alkenyl group, an alkynylene group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, an alkenyl group, an alkynyl group, an alkynyl group, An alkoxy group, an aryl group, and the like, but the present invention is not limited thereto.

The term pattern in the present application may mean a pattern formed by the self-assembling structure of the block copolymer on the surface of the film including the block copolymer, and may mean a pattern including two or more lines.

The present application relates to a pattern forming method. The pattern forming method of the present application includes atomic layer deposition (ALD) deposition on the polymer film of a substrate on which a self-assembled polymer film including a polymer segment A and a polymer segment B different from the segment A is formed, To form a metal-containing layer. It is possible to improve the etching resistance of the film including the block copolymer by forming the metal containing layer on the polymer film, and it is possible to prevent the structure from being broken during the etching.

The Atomic Layer Deposition (ALD) utilizes a vapor phase chemical vapor deposition (CVD) process, but precursors and reactants are injected in a time-division manner to suppress the gas phase reaction and self- limited reaction may be used to precisely control the thickness of the thin film. Atomic layer deposition proceeds in a cycle. Generally, one growth cycle consists of four stages: ① precursor supply ② purge ③ reactant supply ④ purge. These four steps are the basic cycle for thin film growth, and the cycle of atomic layer deposition technology is repeated for the required thickness deposition during thin film formation. Therefore, the atomic layer deposition technique can control the thickness of the thin film precisely 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. The fact that the metal-containing layer is formed substantially on only one segment of the block copolymer means that a metal-containing layer is formed on the polymer segment of any one of the polymer segment A and the polymer segment B at an area ratio of 90% or more, May mean that the metal-containing layer is formed at an area ratio of 10% or less. For example, when the metal-containing layer is formed substantially only on the polymer segment A, the metal-containing layer may contain at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95% %, 97%, 98%, 99%, or 100%, but is not limited thereto. In this case, the metal-containing layer is formed on the polymer segment B in an amount of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, Or 0%, but is not limited thereto. When the metal-containing layer is formed substantially only on the polymer segment B, the metal-containing layer has 90% or more, 91% or more, 92% or more, 93% or more, 94% , At least 97%, at least 98%, at least 99%, or at least 100%, but is not limited thereto. In this case, the metal-containing layer is formed on the polymer segment A in an amount of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, Or 0%, but is not limited thereto. As described above, by forming the metal-containing layer only in the polymer segment A or only in the polymer segment B, a metal-containing layer can be selectively formed in a specific block of the block copolymer, and a metal- A metal-containing layer can be selectively formed in the pattern. This makes it possible to secure the etching selectivity to the self-assembled structure of the block copolymer, and it can exhibit the etching selectivity even when the polymer segment A and the polymer segment B contained in the block copolymer share a specific chemical structure.

In one example, the polymer segment A of the block copolymer according to the present application may comprise a unit of the following general formula (1).

[Chemical Formula 1]

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) (= O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and Y is -X ₁ - or -X ₁ -C (= O) -, wherein X ₁ is an oxygen atom, a sulfur atom, Is a monovalent substituent group including a ring structure having a chain having 8 or more chain forming atoms connected thereto.

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

The monovalent substituent of Y in formula (1) includes a chain structure formed by at least eight chain-forming atoms.

The term chain forming atom in the present application means an atom forming a straight chain structure of a certain chain. The number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and the number of the other atoms bonded to the chain-forming atoms (for example, the chain- A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not calculated. Also, in the case of a branched chain, the number of chain-forming atoms can 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, the number is 5, and even if the chain is a 2-methylpentyl group, all the chain-forming atoms are carbon, The chain-forming atom may be exemplified by carbon, oxygen, sulfur or nitrogen, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of the chain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

The unit of the formula (1) can make the block copolymer exhibit excellent self-assembling 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 optionally be substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted by another substituent.

In Formula (1), Y may include a cyclic structure, and the chain may be connected to the cyclic structure. Such a ring structure can further improve the self-assembling property and the like of the block copolymer formed by the monomer. 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. The linker is an oxygen atom, a sulfur _{atom, -NR 1 -, S (=} O) 2 -, a carbonyl group, an alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or - X ₁ -C (= O) -, etc., wherein R ₁ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, X ₁ represents a single bond, , -NR ₂ -, -S (═O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and R ₂ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, have. An appropriate linker may be an oxygen atom or a nitrogen atom. The chain may be connected to the 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 may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group).

Y in the formula (1) may be represented by the following formula (2) in one example.

(2)

In the formula 2 P is an arylene group, Q is a single bond, an oxygen atom or -NR ₃ - and, at the R ₃ is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group or aryl group, Z is 8 Or more of the chain forming atoms. When Y in the general formula (1) is a substituent of the general formula (2), P in the general formula (2) may be directly connected to X in the general formula (1).

Suitable examples of P in formula (2) include, but are not limited to, an arylene group having 6 to 12 carbon atoms, such as a phenylene group.

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

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

Accordingly, examples of suitable examples of the formula (1) include the following formula (3).

(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, Z is a chain- Lt; RTI ID = 0.0 > 8 < / RTI >

The block copolymer of the present application may contain units represented by the general formulas (1), (2) and / or (3) to exhibit excellent self-assembling properties of the block copolymer, To form a lamellar structure.

In one example, the metal-containing layer of the present application can be formed at < RTI ID = 0.0 > 125 C < / RTI > The formation temperature of the metal-containing layer is preferably not less than 127 占 폚, not less than 129 占 폚, 131 占 폚 or more, 133 占 폚 or more, 135 占 폚 or more, 137 占 or more, 139 占 or more, 141 占 or more, 143 占 or more, Or more, 148 占 폚 or more, or 150 占 폚 or more. The upper limit of the temperature is not particularly limited as long as it is the thermal decomposition temperature of the precursor or the structural deformation temperature (ODT) of the block copolymer, and may be different depending on the kind of precursor or block copolymer used. The upper limit of the temperature may be, for example, not more than 350 占 폚 or not more than 300 占 폚, but is not limited thereto.

The formation temperature of the metal-containing layer may be the temperature of the third reactor in the growth cycle of the atomic layer deposition described above. The metal-containing layer may grow through the reduction reaction of the metal compound of the precursor forming the metal-containing layer. When the formation temperature of the metal-containing layer satisfies the above range, the metal-containing layer may be formed only in the polymer segment A, Or only the polymer segment B can be formed. The temperature range may be the same in the (1) precursor supply, (2) purging and / or (4) purge steps during the growth cycle of atomic layer deposition.

In one example of the present application, by applying an ALD process in the temperature range on a film formed from a block copolymer containing a unit represented by the above formula (1), a metal-containing layer is formed substantially only on the polymer segment A Can be controlled. In this case, the metal-containing layer is formed on the polymer segment A by 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% , 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, or 2% or less of the metal- Or less, or 1% or less, but is not limited thereto.

In another example of the present application, the metal containing layer formed by atomic layer deposition may be incorporated into the polymer film. The presence of the metal-containing layer in the polymer film may mean a state in which a part of the polymer film is deformed so as to include a metal-containing layer by forming a metal-containing layer after the precursor forming the metal-containing layer penetrates into the polymer film. Therefore, when the metal-containing layer is formed only in the polymer segment A as described above, a metal-containing layer may be formed on the polymer segment A, and a metal-containing layer may be mixed in the polymer segment A to deform a part of the polymer segment A. When a metal-containing layer is formed only in the polymer segment B, a metal-containing layer may be formed on the polymer segment B, and a metal-containing layer may be incorporated in the polymer segment B to deform a part of the polymer segment B. When the metal-containing layer is incorporated into 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 incorporating the metal-containing layer into the polymer membrane to modify a part of the polymer membrane is not particularly limited as long as a metal-containing layer is formed on the polymer membrane and a part of the polymer membrane can be deformed. Examples thereof include Sequential Infiltration Synthesis , SIS) method can be used.

In one example of the present application, the precursor forming the metal-containing layer can exhibit affinity with the compound contained in the polymer segment A or the polymer segment B of the block copolymer. The precursor has an affinity with a compound contained in the polymer segment means that the physical and / or chemical properties between the metal compound contained in the precursor and the compound included in the polymer segment cause the precursor and the polymer segment to have physical and / It can mean that there is a force to form bonds, bonds, and contacts. The kind of the force due to the physical and / or chemical properties between the metal compound contained in the precursor and the compound contained in the polymer segment is not particularly limited as long as it exists between the metal compound of the precursor and the compound contained in the polymer segment, For example, it can 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, the affinity for different components is a relative concept, and it can be expressed that a component having a larger affinity is more affinity than other components. When the precursor has an affinity with a compound contained in the polymer segment A, the metal-containing layer can be formed only on the polymer segment A of the block copolymer. When the precursor has affinity with the compound included in the polymer segment B, Containing layer may be formed only on the polymer segment B of the block copolymer. For example, when 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 may be different from the affinity between the precursor and the polymer segment A The metal-containing layer can be formed only on the polymer segment B. As described above, since the precursor and the compound included in the polymer segment have affinity, the precursor can be adsorbed only to the polymer segment A or adsorbed only to the polymer segment B during the step of supplying the precursor in the growth cycle of atomic layer deposition.

The precursor forming the metal-containing layer of the present application may be at least one selected from the group consisting of (organic) metal compounds, (organic) metal complexes, (organic) metal clusters, metal nanoparticles, metal particles or pieces, . ≪ / RTI > The precursor may be, for example, an organometallic compound and the precursor may be aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, rhodium, iridium, 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, But is not limited thereto. The precursor may vary depending on the kind of the block copolymer to be formed with the metal-containing layer. For example, TMA (trimethylaluminum) and DEZ (diethylzinc) may be used.

The pattern forming method of the present application may further include the step of selectively removing any one of the polymer segments of the block copolymer forming the self-assembled structure after forming the metal-containing layer. The method of selectively removing one 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 light, (Inductively Coupled Plasma) etching or Reactive Ion Etching (RIE) may be used. For example, a polymer segment of a block copolymer may be selectively removed by reactive ion etching . The reactive ion etching may be performed according to a known method, and the etching conditions are not particularly limited. For example, argon or oxygen may be used as a reactive gas.

The pattern forming method of the present application may further include the step of etching the substrate using the polymer film from which a polymer segment has been removed as a mask. The step of selectively etching the substrate using the polymer membrane having the polymer segment removed as a mask is not particularly limited and may be performed by, for example, a reactive ion etching step using CF ₄ / Ar ions or the like, Removing the polymer film from the substrate by an oxygen plasma treatment or the like, and removing the metal containing layer using reactive ion etching or the like.

The block copolymer of the present application may be embodied in a periodic structure including a sphere, a cylinder, a gyroid or a lamellar through self-assembly. In the case of spores or lamellas of the above structures, the block copolymer may be present in a vertically oriented state.

In one example, the polymer segment B of the block copolymer of the present application may comprise a unit represented by the following formula (4).

[Chemical Formula 4]

In formula 4 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - and, in the X ₁ is a single bond, oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenyl group or alkynyl group, and W is at least one halogen 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 at least 2, at least 3, at least 4, or at least 5 halolene atoms.

The polymer segment B contained in the block copolymer may include a unit represented by the following formula (5).

[Chemical Formula 5]

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

X ₂ in Formula 5 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 each independently represents a hydrogen atom, an alkyl group, a haloalkyl group or a halogen atom, and R ₁ to R ₅ each independently represent one or more, two or more, three or more, four or more, , For example, a fluorine atom. The halogen atoms contained in R ₁ to R ₅ , for example, the fluorine atom, 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 includes the units of the above formula (4) or (5), so that the block copolymer exhibits excellent self-assembling properties.

The present application also relates to a laminate. The laminate of the present application comprises a substrate; A self-assembled polymer membrane formed on the substrate and comprising a block copolymer comprising a polymer segment A and a polymer segment B different from the segment A; And a metal-containing layer, and a 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 the formula (1), and the polymer segment B may include a unit represented by the formula (4). The self-assembled structure of the block copolymer may also be a cylinder, sphere or lamellar structure. The details of the block copolymer, polymer segment A, B, metal-containing layer, etc. included in the laminate of the present application are the same as those described in the above-described pattern formation method, and will be omitted.

A specific method for producing such a block copolymer in the present application 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 the LRP (Living Radical Polymerization) method using the above monomers. For example, anionic polymerization in which an organic rare earth metal complex is used as a polymerization initiator, or an organic alkali metal compound is used as a polymerization initiator in the presence of an inorganic acid salt such as a salt of an alkali metal or an alkaline earth metal, An atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization initiator, and an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Initiators for Continuous Activator Regeneration (ATR), Atomic Transfer Radical Polymerization (ATRP), Inorganic Reducing Agent Reversible Additive - Reversible addition-cleavage chain transfer using cleavage chain transfer agent 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 can be prepared in a manner that includes polymerizing a reactant containing monomers capable of forming the block in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization .

The method of forming the other block included in the copolymer together with the block formed by using the monomer in the production of the block copolymer is not particularly limited and may be appropriately selected in consideration of the kind of the desired block, Block can be formed.

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

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

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

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

The present application provides a pattern forming method and a laminate capable of preventing breakdown of structures and defects in shape while imparting etching selectivity to etching a block copolymer forming a self-assembled structure.

FIG. 1 is an SEM image showing the result of Example 1 in which alumina is formed only in the polymer segment A. FIG.
Fig. 2 is an SEM image after removing the polymer segment B in Example 1. Fig.
Fig. 3 is an 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. Fig.

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

Production Example 1. Synthesis of monomer (A)

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

4-dodecyloxyphenol (9.8 g, 35.2 mmol) synthesized in the flask, methacrylic acid (6.0 g, 69.7 mmol) DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol) And DMAP (p-dimethylaminopyridine) (1.7 g, 13.9 mmol) was added, 120 mL of methylene chloride was added, and the reaction was allowed to proceed at room temperature under nitrogen for 24 hours. After completion of the reaction, the salt (urea salt) produced during the reaction was filtered off and the remaining methylene chloride was removed. The resulting product was recrystallized in a mixed solvent of methanol and water (1: 1 mixture) to obtain the title compound (7.7 g, 22.2 mmol) as a white solid. 1H-NMR (DMSO-d6) 63%. ≪ / RTI >

(A)

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

Production Example 2. Synthesis of block copolymer (A-1)

2.0 g of the monomer (A) of Preparation Example 1, 64 mg of cyanoisopropyldithiobenzoate as a reversible addition fragmentation chain transfer (RAFT) reagent, 23 mg of azobisisobutyronitrile (AIBN) as a radical initiator and 5.34 mL of benzene were dissolved in 10 mL of Schlenk flask , And the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition Fragmentation Chain Transfer (RAFT) at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to give a giant initiator of pink color. The yield of the macromonomer was about 82.6% by weight and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 9,000 and 1.16, respectively. 0.3 g of macroinitiator, 2.7174 g of pentafluorostyrene monomer, and 1.306 mL of benzene were placed in a 10 mL Schlenk flask and stirred at room temperature for 30 minutes under a nitrogen atmosphere. Reversible Addition Fragmentation Chain Transfer (RAFT) Respectively. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The block copolymer includes a polymer segment A derived from the monomer (A) of Production Example 1 and having 12 chain-forming atoms (the number of carbon atoms of R in Formula A) and a polymer segment B derived from the pentafluorostyrene monomer .

Production Example 3. Synthesis of block copolymer (A-2)

2.0 g of the monomer (A) of Preparation Example 1, 42.6 mg of cyanoisopropyl dithiobenzoate as a Reversible Addition Fragmentation chain transfer (RAFT) reagent, 3.2 mg of azobisisobutyronitrile (AIBN) as a radical initiator and 4.77 g of anisole were dissolved in 10 mL of Schlenk flask, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition Fragmentation Chain Transfer (RAFT) at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to give a giant initiator of pink color. The yield of the macro initiator was about 73.3 wt%, and the number average molecular weight (Mn) and the 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 placed in a 10 mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition Fragmentation Chain Transfer (RAFT) Respectively. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The block copolymer includes a polymer segment A derived from the monomer (A) of Production Example 1 and having 12 chain-forming atoms (the number of carbon atoms of R in Formula A) and a polymer segment B derived from the pentafluorostyrene monomer .

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

TMA (trimethylaluminum) was poured into the vertically oriented lamellar structure-forming block copolymer for 120 seconds and purged in a nitrogen atmosphere. The purging proceeded at a flow rate of 50 sccm for 600 seconds at a pressure of 1.6 Torr. After purging, water was poured for 120 seconds and then purged under nitrogen atmosphere under the same conditions. The whole process was carried out at 150 ° C. The result of the alumina formation in the block copolymer after repeating the cycle 10 times was confirmed by SEM. 1 shows the result of forming alumina only in the polymer segment A as a result of the first embodiment.

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

As shown in FIG. 2, the structure of the polymer segment A was permeated with alumina to exhibit etching resistance, and alumina was incorporated after etching.

Example 2

A lamellar pattern formed by coating the block copolymer (A-2) on any untreated silicon substrate and thermally annealing at 160 캜 for 1 hour was confirmed by SEM. The pitch of the formed lamellar pattern was confirmed to be 15.6 nm. The block copolymer (A-2) used here was characterized by being vertically oriented on any unprocessed substrate and horizontally oriented on the substrate on which the composition for forming a guide pattern was formed. As a result of observation through a SEM, a vertically oriented lamellar structure Was observed.

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

As shown in FIG. 3, the structure of the polymer segment A was permeated with alumina to exhibit etching resistance, and alumina was mixed even after etching.

Example 3

The trench substrate was prepared in the following manner. A silicon wafer was used as the substrate. On the substrate, a layer of SiO 2 was formed to a thickness of about 200 nm by a known deposition method. Subsequently, a bottom anti-reflective coating (BARC) was coated on the SiO 2 layer to a thickness of about 60 nm, and a PR (positive-tone resist) layer was coated thereon to a thickness of about 400 nm . Then, the PR layer was patterned by a KrF stepper exposure method. Subsequently, using the patterned PR layer as a mask, the BARC layer and the SiO layer were etched by RIE (Reactive Ion Etching) method, and the residue was removed to form a trench structure.

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

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

As shown in FIG. 4, the structure of polymer segment A was permeated with alumina to exhibit etching resistance, and alumina was incorporated after etching.

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. As a result, it was confirmed that alumina was formed in both the polymer segment A and the polymer segment B.

6 is an SEM image showing a result of performing reactive ion etching on a substrate on which alumina is formed on both the polymer segment A and the polymer segment B. FIG. As shown in FIG. 4, it was confirmed that the etching selectivity was lowered and defects were formed in the post-etching structure.

Comparative Example 2

Experiments were 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, which is an SEM image showing the result of performing reactive ion etching on a substrate on which alumina is formed on both the polymer segment A and the polymer segment B. FIG. As shown in FIG. 7, it was confirmed that the etching selectivity was lowered and defects were generated in the post-etching structure.

Claims (17)

A metal-containing layer is formed by atomic layer deposition (ALD) on the polymer film of the substrate on which the self-assembled polymer membrane including the polymer segment A and the block copolymer having the polymer segment B different from the segment A is formed To form a pattern.
The pattern forming method according to claim 1, wherein the metal-containing layer is formed on the segment of the polymer segment A or the polymer segment B of the self-assembled polymer film at an area ratio of 90% or more, and the pattern formation Way.
The pattern forming method according to claim 1, wherein the polymer segment A comprises a unit represented by the following formula (1), and the ALD process is performed at 130 ° C or higher:
[Chemical Formula 1]

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) (= O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and Y is -X ₁ - or -X ₁ -C (= O) -, wherein X ₁ is an oxygen atom, a sulfur atom, Is a monovalent substituent group including a ring structure having a chain having 8 or more chain forming atoms connected thereto.
The pattern forming method according to claim 3, wherein the metal-containing layer is formed at an area ratio of 90% or more on the polymer segment A and the area ratio is 10% or less on the polymer segment B.
The method according to 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 selected from the group consisting of organometallic compounds, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, A metal compound such as iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, gallium, indium, thallium, tin, lead and bismuth; ≪ / RTI > wherein the metal compound comprises at least one species of metal.
The method of claim 1, further comprising selectively removing any polymer segment of the block copolymer forming the self-assembled structure after formation of the metal-containing layer.
8. The method of claim 7, wherein removing one of the polymer segments uses reactive ion etching.
9. The method of claim 8, wherein the reactive ion etching uses argon or oxygen.
The pattern forming method according to claim 7, further comprising the step of etching the substrate using the polymer film from which a polymer segment 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 lamellar structure.
The pattern forming method according to claim 1, wherein the polymer segment B of the block copolymer comprises a unit represented by the following formula (4)
[Chemical Formula 4]

In formula 4 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - and, in the X ₁ is a single bond, oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenyl group or alkynyl group, and W is at least one halogen Is an aryl group containing an atom.
Board; A self-assembled polymer membrane formed on the substrate and comprising a block copolymer comprising a polymer segment A and a polymer segment B different from the segment A; And a metal-containing layer,
Wherein the metal-containing layer is formed on at least one of the polymer segment A and the polymer segment B of the self-assembled polymer membrane at an area ratio of 90% or more, and the other segment has a metal- .
14. The laminate according to claim 13, wherein the polymer segment A comprises a unit represented by the following formula (1)
[Chemical Formula 1]

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) (= O) ₂ -, an alkylene group, an alkenylene group or an alkynylene group, and Y is -X ₁ - or -X ₁ -C (= O) -, wherein X ₁ is an oxygen atom, a sulfur atom, Is a monovalent substituent group including a ring structure having a chain having 8 or more chain forming atoms connected thereto.
14. The laminate according to claim 13, wherein the polymer segment B comprises a unit represented by the following formula (4): < EMI ID =
[Chemical Formula 4]

In formula 4 X ₂ is a single bond, an oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenylene group, alkynylene _{group, -C (= O) -X 1} - or -X ₁ -C (= O) - and, in the X ₁ is a single bond, oxygen atom, sulfur _{atom, -S (= O) 2 -} , alkylene group, alkenyl group or alkynyl group, and W is at least one halogen Is an aryl group containing an atom.
14. The laminate of claim 13, wherein the self-assembled structure of the block copolymer is a cylinder, sphere or lamellar structure.
14. The method of claim 13, wherein the metal compound is selected from the group consisting of aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, And at least one member 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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