KR20180121204A - Method of producimg layer structure, and method of forming patterns - Google Patents

Abstract

According to an embodiment of the present invention, provided is a film structure manufacturing method including the steps of: forming a first organic layer by applying a first composition on a substrate with a plurality of patterns and then curing the first composition (S1); removing a part of the first organic layer by applying a liquid material to the first organic layer (S2); and forming a second organic layer by applying a second composition on the first organic layer which is partially removed and then curing the second composition (S3). Each of the first and second compositions independently includes a polymer including a structure unit represented by chemical formula 1, a monomer including a ring group with a molecular weight of 1,500 or less and at least three substituted or unsubstituted benzene rings in a structure thereof, and a solvent. Accordingly, the present invention can improve corrosion resistance and planarization.

Description

[0001] METHOD OF PRODUCING LAYER STRUCTURE, AND METHOD OF FORMING PATTERNS [0002]

And more particularly, to a method for fabricating a multi-pattern structure such as a dual damascene wiring structure and a pattern forming method using the same.

BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.

In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer.

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.

Further, in the case where there is a step on the substrate to be processed in the multiple patterning process, or in the case where the pattern density portion and the patternless region are present together on the wafer, the hard mask layer filled in the pattern has a planarization characteristic This is especially important.

Therefore, a film structure capable of satisfying the above-mentioned characteristics is required.

One embodiment of the present invention is a method of manufacturing a film structure which exhibits excellent planarization characteristics without a separate etchback process or a CMP (Chemical Mechanical Polishing) process and which uses predetermined polymers and monomers as a film material to improve corrosion resistance and planarization .

Another embodiment provides a method of forming a pattern using a film structure according to the above manufacturing method.

According to one embodiment, a method of manufacturing a semiconductor device, comprising: (S1) applying a first composition onto a substrate having a plurality of patterns and curing the first composition to form a first organic layer; Applying a liquid material to the first organic layer to remove a portion of the first organic layer (S2); (S3) applying a second composition on the first organic layer from which a part of the first organic layer has been removed and curing the first organic layer to form a second organic layer, wherein the first composition and the second composition each independently have the following formula A monomer containing a cyclic group having a molecular weight of 1,500 or less and at least three substituted or unsubstituted benzene rings in its structure, and a solvent.

The first organic layer partially removed may remain in the gap of the pattern.

The liquid substance may be at least one selected from the group consisting of? -Butyrolactone,? -Valerolactone, ethyl lactate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether acetate,? -Hydroxy? Butylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, Ethylene glycol monomethyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, poly (ethylene glycol), propylene glycol Glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate Propyleneglycol monomethyl ether propionate, ethyleneglycol diacetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, formamide, monomethyl formate Amide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, N-methylpyrrolidone, methoxymethylpropionate, methoxyethylpropionate, Ethoxyethyl propionate, ethoxypropyl propionate, ethoxybutyl propionate, dimethyl sulfone, dimethyl sulfoxide, sulfonic acid, isopropoxy propionate, methoxy propionate, ethoxy methyl propionate, ethoxy ethyl propionate, Acetone, acetyl acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. Can.

The liquid material may be applied in a content ranging from 0.1 cc to 100 cc.

The first organic layer and the second organic layer may be a hard mask layer.

The second organic layer may be formed directly on the first organic layer from which a part of the organic layer is removed.

The monomers may each independently include a monovalent to trivalent cyclic group derived from a substituted or unsubstituted cyclic group selected from the following Group 1.

[Group 1]

In the group 1,

Z ¹ represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,

Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.

The molecular weight of the monomer may independently be 500 or more and 1,300 or less.

The monomer may comprise a ring group fused with at least four substituted or unsubstituted benzene rings.

At least one of the monomers may be represented by any one of the following formulas (1-1) to (1-6).

[Formula 1-1]

In Formula 1-1,

A is a substituted or unsubstituted aromatic ring group,

X ¹ , X ² and X ³ are each independently a monovalent group derived from substituted or unsubstituted indole,

Y ¹ , Y ² and Y ³ are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C20 alkyl An amino group, or a substituted or unsubstituted C1 to C30 alkoxy group,

m ¹ , m ² , m ³ , n ¹ , n ² and n ³ are each independently 0 or 1.

However, m ^1, m ² and m ^3, at least one is 1, and when m ¹ is 0, n ¹ is 0, when m ² is 0 and n ² is 0, m ³ is 0, n ³ is 0:

[Formula 1-2]

In Formula 1-2,

T is a triazine or triazine derivative,

R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.

Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group:

[Formula 1-3]

In Formula 1-3,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

k and l are each independently 0 or 1, satisfying 1? k + 1? 2,

m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,

p and q are each independently an integer of 1 or more and satisfy 1? p + q? (the maximum number of substituents that A0 can have)

[Formula 1-4]

In Formula 1-4,

A ¹ is An aliphatic cyclic group or an aromatic cyclic group,

A ² To A < ⁴ > each represent a benzene group,

X ¹ to X ³ each independently represent a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,

M is CR ^a , SiR ^b , N, P, PR ^c R ^d or PR ^e ,

n is an integer of 1 to 4,

Wherein R ^a , R ^b , R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

R ^e is oxygen (O) or sulfur (S):

[Formula 1-5]

In Formula 1-5,

A ¹ to A ³ each independently represents an aliphatic cyclic group or an aromatic cyclic group,

X ¹ to X ³ each independently represent a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,

n is an integer from 3 to 5,

m is an integer from 1 to 3;

[Chemical Formula 1-6]

In the above formulas 1-6,

A ⁰ and A ¹ are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

X is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

Y is a boron (B) -containing group,

n is an integer of 1 to 5;

In Formula 1, A ¹ may be a divalent cyclic group including at least two rings in its structure.

In Formula 1, A ¹ may be any of the substituted or unsubstituted moieties listed in Groups 2 and 3 below.

[Group 2]

In the group 2,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl:

[Group 3]

In the group 3,

R ⁰ and R ¹ are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, It is a combination.

B ¹ in the formula (1) may be represented by the following formula (3).

(3)

In Formula 3,

a and b are each independently an integer of 0 to 2,

L is any one of the substituted or unsubstituted moieties listed in Group 2 below, or any of the groups listed in Group 4 below.

[Group 2]

In the group 2,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl:

[Group 4]

In Group 4 above,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,

Y ¹ and Y ² are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, or at least one of the combinations thereof are Y ¹ and Y ² is a substituted or An unsubstituted C6 to C30 aryl group,

Z ⁷ to Z ¹⁰ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group , A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,

g, h, i and j are each independently an integer of 0 to 2,

k is an integer of 1 to 3,

"*" Is the connection point.

In the group 4, X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, and the C6 to C50 arylene group may be any one of the moieties listed in Group 5 below.

[Group 5]

The polymer may include two or more different structural units represented by the general formula (1).

The curing process after applying the second composition may proceed at a higher temperature than the curing process after applying the first composition.

The first composition and the second composition may each independently comprise a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), a photoacid generator (PAG), or a combination thereof.

The crosslinking agent may be selected from the group consisting of methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, Methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination thereof.

The solvent contained in the first composition and the solvent included in the second composition are each independently selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) Propyleneglycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone Para, methyl pyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, or combinations thereof.

The first composition and the second composition may each independently be applied in a thickness of 300 A to 10 mu m.

According to another embodiment, one surface of the substrate includes a first portion having a plurality of patterns and a second portion having no pattern, and the second organic layer step sum (S3) is a sum of the first organic layer step sum (S1 ). ≪ / RTI >

Providing a membrane structure made according to the method described above; Forming a silicon-containing thin film layer on the film structure; Forming a photoresist layer on the silicon-containing thin film layer; Exposing and developing the photoresist layer to form a photoresist pattern; And selectively removing the silicon-containing thin film layer and the first organic layer, the second organic layer, or a combination thereof in the film structure using the photoresist pattern.

And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.

It is advantageous to realize a semiconductor fine pattern because it provides a film structure excellent in step characteristics without a separate planarization process such as etchback or CMP. In addition, corrosion resistance and solubility can be secured at the same time by blending a predetermined polymer and a monomer as a film structure material and using it as a film material.

FIG. 1 is a flowchart illustrating a method of manufacturing a membrane structure according to an embodiment,
2 is a cross-sectional view exemplarily showing a step of the first organic layer,
FIGS. 3 to 5 are cross-sectional views illustrating a state in which a part of the first organic layer of FIG. 2 is removed,
6 is a cross-sectional view showing the step of the second organic layer,
7 to 9 are sectional views for explaining a pattern forming method according to an embodiment,
10 is a reference diagram for explaining the step 1 for evaluating the planarization characteristic,
11 is a reference diagram for explaining the step 2 for evaluating the planarization characteristic.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

The singular forms used in this specification include plural forms unless the context clearly dictates otherwise. The word " comprises " and / or " comprising ", as used herein, refers to features, integers, steps, operations, Elements, components, and / or components, but does not preclude the addition of one or more other aspects, numbers, steps, operations, component elements, and / or sets thereof.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.

Further, in the present specification, the "monovalent group derived from the A compound" means a monovalent group formed by substitution of one hydrogen in the A compound. For example, a monovalent group derived from a benzene group is a phenyl group. Further, the term "bivalent group derived from A compound" means a bivalent group in which two hydrogen atoms in A compound are substituted to form two connecting points. For example, a divalent group derived from a benzene group becomes a phenylene group.

Hereinafter, a method of manufacturing a membrane structure according to one embodiment will be described with reference to FIG.

1 is a flowchart illustrating a method of manufacturing a membrane structure according to an embodiment.

Referring to FIG. 1, the method for fabricating a film structure includes: (S1) forming a first organic layer by applying a first composition on a substrate having a plurality of patterns and curing the first composition; Applying a liquid material to the first organic layer to remove a portion of the first organic layer (S2); And applying a second composition to the first organic layer on which a part of the organic layer has been removed and curing it to form a second organic layer (S3).

In the step (S1) of forming the first organic layer, the substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. Alternatively, the substrate may be a silicon substrate, a silicon nitride, a TiSi, a silicide, a polysilicon tungsten, copper, aluminum, TiN, TaN or a combination thereof on a glass substrate or a polymer substrate.

The substrate has a plurality of patterns on one surface, and the shape of the pattern is not limited to a triangle, a square, a circle, and the like. The average size (length, width) of the patterns may be, for example, several nanometers to several hundred nanometers, and the average size (length, depth) of the patterns may be several tens of micro Meter. In this specification, 'gap of a pattern' or 'gap of a pattern' means an empty space formed between a first pattern and a second pattern adjacent thereto, and the average size (width) of the gaps of the plurality of patterns is, for example, May be from a few nanometers to several hundred nanometers and the average size of the pattern (length) may be, for example, from a few nanometers to a few tens of micrometers.

Curing the first composition in step (S1) of forming a first organic layer comprises applying energy to the first composition. The energy includes all possible means for curing the first composition, such as thermal energy, ultraviolet light, microwave, sonic, ultrasonic. The first composition may be further filled with the first composition through a gap between the plurality of patterns through the curing process.

For example, the step of curing the first composition may be carried out, for example, in the range of 20 to 400 ° C.

Hereinafter, the first composition will be described.

The first composition includes a polymer comprising a structural unit represented by the following formula (1), a monomer including a ring group having a molecular weight of 1,500 or less and a benzene ring fused with at least three substituted or unsubstituted benzene rings in the structure, and a solvent.

First, the monomer will be described.

The first composition includes a monomer having a molecular weight in a predetermined range as a solid component so that it can be gap-pilled without voids even to the bottom of a deep pattern. The monomer has at least three substituted or unsubstituted benzene rings By including a fused ring group, excellent corrosion resistance can be exhibited.

The molecular weight of the monomer may be 1,300 or less independently in the above range, and may be, for example, 500 or more and 1,300 or less, but is not limited thereto. Further, the monomers may each independently include, for example, a ring group in which 3, 4 or 5 substituted or unsubstituted benzene rings are fused, and the shape to be fused is not particularly limited.

The monomers may each independently include a plurality of substituted or unsubstituted aliphatic or aromatic ring groups within the structure. The monomers may each independently include monovalent to trivalent organic groups derived from, for example, substituted or unsubstituted cyclic groups selected from the following Group 1.

[Group 1]

In the group 1,

Z ¹ represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,

Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.

The cyclic groups listed in the group 1 are unsubstituted or may be included in the monomers in which at least one hydrogen atom is substituted in these cyclic groups. In this case, the physical properties of the first composition can be controlled by selecting the kind and the number of the substituent, and the functional group is preferably a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 aliphatic group, a substituted or unsubstituted C1 to C20 allyl group, a substituted or unsubstituted C1 to C4 alkyl ether, a substituted or unsubstituted C7 to C20 arylalkylene ether, A borane group, and a substituted or unsubstituted C6 to C30 arylborane group, but the present invention is not limited thereto.

The monomers each independently have a molecular weight of 1,500 or less, and various structural modifications are possible within a range including a ring group in which at least three substituted or unsubstituted benzene rings are fused. For example, at least one of the monomers may be represented by any one of the following formulas (1-1) to (1-6), but is not limited thereto.

[Formula 1-1]

In Formula 1-1,

A is a substituted or unsubstituted aromatic ring group,

X ¹ , X ² and X ³ are each independently a monovalent group derived from substituted or unsubstituted indole,

Y ¹ , Y ² and Y ³ are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C20 alkyl An amino group, or a substituted or unsubstituted C1 to C30 alkoxy group,

m ¹ , m ² , m ³ , n ¹ , n ² and n ³ are each independently 0 or 1.

However, m ^1, m ² and m ^3, at least one is 1, and when m ¹ is 0 and n ¹ is 0, when m ² is 0 and n ² is 0, when m ³ is 0, n ³ is zero.

[Formula 1-2]

In Formula 1-2,

T is a triazine or triazine derivative,

R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.

Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group.

[Formula 1-3]

In Formula 1-3,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

k and l are each independently 0 or 1, satisfying 1? k + 1? 2,

m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,

p and q are each independently an integer of 1 or more and satisfy 1? p + q? (the maximum number of substituents that A0 can have).

[Formula 1-4]

In Formula 1-4,

A ¹ is An aliphatic cyclic group or an aromatic cyclic group,

A ² To A < ⁴ > each represent a benzene group,

X ¹ to X ³ each independently represent a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,

M is CR ^a , SiR ^b , N, P, PR ^c R ^d or PR ^e ,

n is an integer of 1 to 4,

Wherein R ^a , R ^b , R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

R ^e is oxygen (O) or sulfur (S).

[Formula 1-5]

In Formula 1-5,

A ¹ to A ³ each independently represents an aliphatic cyclic group or an aromatic cyclic group,

X ¹ to X ³ each independently represent a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,

n is an integer from 3 to 5,

m is an integer of 1 to 3;

[Chemical Formula 1-6]

In the above formulas 1-6,

A ⁰ and A ¹ are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

X is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

Y is a boron (B) -containing group,

n is an integer of 1 to 5;

The first composition may contain one or more of the above-mentioned predetermined monomers.

The monomers may each independently have at least one hydroxyl group, thionyl group, thiol group, cyano group, amino group, C1 to C10 alkyl group, C6 to C30 aryl group, C1 to C30 alkoxy group, Functional groups. In this case, the solubility of the monomer can be further improved to effectively form a spin-on coating method. In addition, a gap-forming method capable of filling a gap between patterns when formed on a lower film having a predetermined pattern by a spin- The fill characteristics and planarization characteristics are also excellent.

On the other hand, the solvent contained in the first composition is not particularly limited as long as it has sufficient solubility or dispersibility to the monomers contained in the first composition, and examples thereof include propylene glycol, propylene glycol diacetate, methoxypropanediol, (Ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethyl formate Amide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.

The monomer included in the first composition may be included in an amount of about 0.1 to 60% by weight based on the total amount of the first composition. By including the compound in the above range, the thickness, surface roughness and leveling of the first organic layer can be controlled.

Hereinafter, the polymer included in the first composition will be described.

The polymer may include a plurality of structural units each represented by the above-described formula (1), and the plurality of structural units may be the same or different.

For example, in Formula 1, A ^{1 may be} any of the substituted or unsubstituted moieties listed in Group 2, but is not limited thereto.

[Group 2]

In the group 2,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl group.

The polymer may have a rigid property by including a ring group derived from the compound of Group 2 in its structural unit.

For example, in Formula 1, A ¹ may be a divalent cyclic group including at least two rings in its structure.

For example, in Formula 1, A ^{1 may be} any of the substituted or unsubstituted moieties listed in Group 3, but is not limited thereto.

[Group 3]

In the group 3,

R ⁰ and R ¹ are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, It is a combination.

Such a polymer includes a ring group containing a hetero atom such as nitrogen, oxygen, or sulfur, which is derived from the compound of Group 3 in its structural unit, so that the polarity of the polymer is increased by the heteroatom to increase the solubility . In addition, since the polymer contains a hydrocarbon ring group in its structural unit, an organic film using the polymer can secure an excellent film density.

For example, in formula (1), A ¹ is a group in which at least one hydrogen atom is replaced by a hydroxyl group, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C10 alkyl group, a C6 to C30 aryl group, a C1 to C30 alkoxy group, Lt; / RTI > may be substituted by a combination.

For example, the linking group represented by B ¹ in the formula 1 may be represented by the following formula (3).

(3)

In Formula 3,

a and b are each independently an integer of 0 to 2,

L is any one of the substituted or unsubstituted moieties listed in Group 2 below, or any of the groups listed in Group 4 below.

[Group 2]

In the group 2,

M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl:

[Group 4]

In Group 4 above,

X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,

Y ¹ and Y ² are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, or at least one of the combinations thereof are Y ¹ and Y ² is a substituted or An unsubstituted C6 to C30 aryl group,

Z ⁷ to Z ¹⁰ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group , A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,

g, h, i and j are each independently an integer of 0 to 2,

k is an integer of 1 to 3,

"*" Is the connection point.

The polymer can increase the flexibility of the polymer by including such a linking group in its structural unit. This flexible structure not only improves the solubility by increasing the free volume of the polymer but also improves the gap-fill performance and planarization by increasing the reflow during the baking process by lowering the glass transition temperature (T _g ) Lt; / RTI >

For example, in Group 4, X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, and the C6 to C50 arylene groups may be any of the moieties listed in Group 5 below .

 [Group 5]

For example, when one or ^two of Y ¹ and Y ² in the group 4 is a substituted or unsubstituted C 6 to C 30 aryl group, the C6 to C30 aryl group may be substituted with 1 to 3 groups derived from any one of the compounds listed in the group 5 May be a period of time.

For example, the polymer may have a weight average molecular weight of about 500 to 200,000. By having a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.

The organic film composition may include two or more kinds of polymers containing the structural unit represented by the formula (1). When two or more different polymers are blended and used, the intended properties can be more easily realized.

The first composition may further include additives such as a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), and a photoacid generator (PAG).

The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The plasticizer may be selected from, for example, DOP (dioctyl phthalate), DOA (dioctyl adipate), TCP (tricresylphostate), diisocctyl phthalate (DIOP), diheptyl, nonyl phthalate (DINP), diunecyl phthalate Di-2-ethylhexyl sebacate (DIDA), diisooctyl azelate (DIOZ), di-2-ethylhexyl sebacate Triethyl 2-ethylhexyl trimellitate (TOTM), polyethylene gpycol ester, ASE (triethyl phosphate), TTP (triphenyl phosphate), CDP (cresyldephenyl phosphate), tricresyl phosphate alkylsulphonic acid phenyl ester), 3G6 (triethylene glycol dihexanoate), 4g7 (tetraethyleneglycol diheptanoate), ATEC (acetyl triethyl citrate), Tributyl citrate (TBC), trioctyl citrate (ATC), acetyl trioctyl citrate ), TMC (trimethyl citrate), DMAD (dimethyl adipate_, MMAD (monomethyl adipate), DBM (dibutyl maleate), DIBM (2, 2-dinitropropyl) formal, BDNPF (2,2,2-trinitroethyl 2-nitroxyethyl ether) polyethylene glycol, polypropylene, or a combination thereof. It is not.

Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxy Methoxymethylated thiourea, methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination thereof, or a combination thereof. But is not limited thereto.

The crosslinking agent may be represented, for example, by any one of the following formulas (A) to (G), but is not limited thereto.

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

(E)

[Chemical Formula F]

[Formula G]

In Formulas A through G above,

R ³³ to R ⁸⁸ each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, Lt; / RTI >

e, f, g and h are each independently an integer of 1 to 10.

Examples of the thermal acid generators include organic sulfonic acid alkyl ester compounds such as benzoin tosylate and 2-nitrobenzyl tosylate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium dodecylbenzenesulfonate , Bis (4-tert-butylphenyl) iodonium camphor sulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro n-butanesulfonate, bis And onium salt compounds such as trifluoromethane sulfonate and triphenylsulfonium trifluoromethane sulfonate. Further, it is also possible to use 2,4,4,6-tetrabromocyclohexadienone, phenyl-bis (trichloromethyl) -s-triazine and N-hydroxysuccinimide trifluoromethanesulfonate, pyridinium p- Pyridinium p-toluenesulfonate, or a combination thereof may be used, but the present invention is not limited thereto.

Examples of the photoacid generators include triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzylsulfonate (2 , 6-dinitrobenzyl sulfonates, pyrogallol tris (alkylsulfonates), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflate norbornene-dicarboximide-triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyl, But are not limited to, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, norbornene- Norbornene-dicarboximide-nonaflate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate (PFOS), diphenylsulfonium perfluorobutanesulfonate, Diphenyliodonium PFOS, methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS, (N-hydroxysuccinimide PFOS), norbornene-dicarboximide PFOS (PFOS), or a combination thereof. The.

The content of the additive may be selected within a range that can improve not only the solubility but also the gap-fill property and the corrosion resistance of the first composition without changing the optical characteristics of the first composition. For example, May be included as the weight part content.

The first composition may be applied by a spin coating method, a screen printing method, a slit coating method, a dipping method, an ink jet method, a casting method, and a spray method, and the first composition may be applied in a thickness of 300 Å to 10 μm But is not limited thereto.

Next, a step S2 of removing a part of the first organic layer will be described.

A part of the first organic layer is dissolved in the liquid material and is removed and planarized.

The liquid material is not particularly limited as long as it has solubility in an organic compound (that is, the above-mentioned polymer and monomer) contained in the first organic layer. For example, the liquid material can be an organic solvent.

For example, the liquid substance may be at least one selected from the group consisting of? -Butyrolactone,? -Valerolactone, ethyl lactate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether acetate,? -Hydroxy? Or a combination thereof.

For example, the liquid material may include the solvents listed below.

But are not limited to, alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerol, Alcohol-based solvents such as pentanediol, 1,3-butanediol, and 1,4-butanediol;

Ethylene glycol monomethyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, poly (ethylene glycol), propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Ether-based solvents such as tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monobutyl ether;

Such as propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, propylene glycol monomethyl ether propionate, ethylene glycol diacetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate and the like Ester solvents;

Amide solvents such as formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide and N-methylpyrrolidone;

Methoxy propionate, methoxy ethyl propionate, methoxy propyl propionate, methoxy butyl propionate, ethoxy methyl propionate, ethoxy ethyl propionate, ethoxy propyl propionate, and Alkoxy alkyl propionate type solvents such as ethoxy butyl propionate and the like;

Sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfonic acid;

Ketone solvents such as acetone, acetyl acetone, methyl ethyl ketone, and methyl isobutyl ketone.

However, the liquid materials listed above are only illustrative and not restrictive.

For example, the liquid material may be applied in a range of 0.1 cc to 100 cc, and may be applied in a range of, for example, 0.1 cc to 50 cc, 0.1 cc to 10 cc, and 0.1 cc to 5 cc, but is not limited thereto.

For example, the liquid material can be dispensed onto the first organic layer by spin-on coating, screen printing, slit coating, dipping, inkjet, casting or spray coating, It may be repeated about 1 to 10 times in consideration of the degree of removal of the organic layer. The rate of ejection and the number of times can be appropriately selected by those skilled in the art in consideration of the physical properties of the first composition, the material of the substrate, the size of the pattern, and the like.

After the step S2 of removing a portion of the first organic layer, the first organic layer may remain in the gap of the pattern. The remaining first organic layer after the step S2 of removing a portion of the first organic layer may be formed in part or all of the inside of the gap of the pattern.

Next, a step (S3) of forming a second organic layer through a curing process after applying the second composition on the first organic layer from which a part is removed will be described.

The second composition is applied over the remaining first organic layer after removing a portion of the first organic layer.

The second composition includes a polymer containing the structural unit represented by the formula (1), a monomer having a molecular weight of 1,500 or less and a ring group in which at least three substituted or unsubstituted benzene rings are fused, and a solvent.

The content of the polymer, monomer, and solvent contained in the second composition is the same as that of the monomer and the solvent contained in the first composition. The kind of the polymer, monomer, and solvent contained in the first composition may be the same as or different from those of the polymer, monomer, and solvent contained in the second composition.

The second organic layer is formed directly on the first organic layer from which a part of the organic layer is removed, so that the second organic layer can be a hard mask layer together with the first organic layer.

As described above, the hard mask layer may contain a different monomer containing a cyclic group having a molecular weight of 1,500 or less and at least three substituted or unsubstituted benzene rings, and a polymer containing a structural unit represented by the formula (1) And the blended composition is used as a film material. Accordingly, it is excellent in corrosion resistance and solubility in solvents, and is advantageously applied in a spin-on coating method.

The polymer and monomers included in the second composition may be present in an amount of from about 0.1 to 60 % ≪ / RTI > by weight. By including the monomer in the above range, the thickness, surface roughness and leveling of the second organic layer can be controlled.

The second composition may further include additives such as a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), a photoacid generator (PAG), and the kind and content of the additive As described in the description of the first composition.

The second composition may be applied by a spin-on coating method, and the second composition may be applied with a thickness of 300 Å to 10 탆, but the present invention is not limited thereto.

After the second composition described above is applied, a second organic layer is formed through a curing process.

The curing process after application of the second composition may include a process of applying energy to the film structure in a state in which the second composition is applied, and the energy may include a process of curing the second composition such as light energy, heat energy, Possible means include. The second organic layer formed through the curing process may be a hard mask compositional film or sacrificial layer for subsequent pattern formation. For example, the curing process after applying the second composition may proceed at a higher temperature than the curing process after applying the first composition. The curing process after applying the second composition may include first curing proceeding in the range of 20 to 400 ° C and second curing proceeding in the range of 30 to 500 ° C, It is possible to have a value higher than the temperature.

2 is a cross-sectional view exemplarily showing a step of the first organic layer. Referring to FIG. 2, although the first composition is filled in the gap, irregularities remain on a part of the surface of the film.

FIGS. 3 to 5 are cross-sectional views illustrating a state in which a part of the first organic layer of FIG. 2 is removed. As shown in Fig. 3, the surface of the film structure in which part of the first organic layer is removed may have a pattern portion having a plurality of patterns and a first organic layer remaining on the top of the non-pattern portion having no pattern, As shown in FIG. 5, a part of the gap of the pattern is filled with the first organic layer (h12> h11? 0), or the entire gap of the pattern is filled with the first organic layer And may be in a form in which the first organic layer is not left on the pattern portion.

The film structure formed by the above-described method can minimize the occurrence of film surface step differences.

6 is a cross-sectional view showing a step of a second organic layer formed on an upper portion of the first organic layer partially removed according to an embodiment.

Referring to FIGS. 2 and 6, the step sum of the surface of the film structure in the state of the second organic layer, that is, │h0 "-h1" │ + │h0 "-h2" │ + │h0 "-h3" │ + │h0 " h4 " is the sum of the surface levels of the film structure in the state of the first organic layer not subjected to the planarization process, that is, the part of which has not been removed, that is, | h0-h1 | + | h0-h2 | + | h0-h3 | + | Compared to -h4, it has a smaller value. That is, it can be seen that the planarization characteristic of the final film structure formed after the planarization process using the liquid material is improved.

According to another embodiment, there is provided a membrane structure produced according to the above-described manufacturing method.

In the film structure, the first organic layer and the second organic layer may be a hard mask layer. Since the hard mask layer has excellent planarization characteristics, it is possible to minimize the CD error of the pattern in the subsequent pattern formation process and improve the CD uniformity of the pattern.

Hereinafter, a method of forming a pattern according to another embodiment will be described with reference to FIGS.

7 to 9 are sectional views for explaining a pattern forming method according to an embodiment.

The pattern formation method may include providing the above-described film structure; Forming a silicon-containing thin film layer on the second organic layer of the film structure; Forming a photoresist layer on the silicon-containing thin film layer; Exposing and developing the photoresist layer to form a photoresist pattern; And selectively removing the silicon-containing thin film layer and the first organic layer, the second organic layer, or a combination thereof in the film structure using the photoresist pattern.

Referring to FIG. 7, the organic layer 120 may be the first organic layer and / or the second organic layer described above, and is formed on the substrate 110 to fill the gap G of the pattern. Forming a silicon-containing thin film layer 130 and a photoresist layer 150 sequentially on the film structure 100 and forming a bottom anti-reflective layer (BARC) 140 before forming the photoresist layer 150 As shown in FIG. Further, the method may further include forming a material layer on the substrate before forming the first organic layer (not shown). The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.

For example, the silicon-containing thin film layer 130 may comprise SiCN, SiOC, SiON, SiOCN, SiC, SiN, or combinations thereof.

Referring to FIG. 8, the photoresist layer is exposed and developed to form a photoresist pattern. The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV, but is not limited thereto. Further, after the exposure, the heat treatment process may be performed at about 100 to 500 ° C.

Referring to FIG. 9, the silicon-containing thin film layer 130 and the organic layer 120 in the film structure are selectively removed. A material layer (not shown) may be formed prior to the formation of the organic layer 120 and a portion of the material layer exposed by the step of selectively removing the silicon-containing thin film layer 130 and the organic layer 120 in the film structure may be etched .

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Synthetic example

Synthetic example  One

[Reaction Scheme 1]

A monomer is synthesized according to Reaction Scheme 1 above.

In a 250 ml two-necked flask equipped with a mechanical stirrer and a cooling tube, 10 g (1 eq.) Of pyrene and 22 g (2 eq.) Of bromobenzoyl chloride were added to 1,2-dichloroethane -dichloroethane (150 g) and stirred well. After 15 minutes, 14 g (2.15 eq.) Of AlCl ₃ was slowly added and the reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction solution was added to methanol, and the precipitated substance was filtered to remove trichloroaluminum and dried.

6.9 g (2.2 eq.) Of bis (pinacolato diboron), 7 g (1 eq.) Of the synthesized solid and 1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium 0.5 g (0.06 equivalents) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (PdCl ₂ (dppf)) and 7.3 g (6 equivalents) of potassium acetate were dissolved in 70 mL of dioxane ) And placed in a 250 ml two-necked flask equipped with a mechanical stirrer and a cooling tube. This was stirred at 80 ° C for 3 hours to conduct the reaction. After completion of the reaction, the reaction product was cooled and purified by filtration through silica gel.

4.5 g (1 eq.) Of the purified yellow solid was dissolved in 40 mL of THF. To this was added 10 mL of H ₂ O and 8.7 g (6 eq.) Of sodium periodate and stirred in a 100 mL round bottom flask . After 30 minutes, 15 mL of 1M HCl was added and stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was extracted with H ₂ O and ethyl acetate, and the organic solvent was removed by reduced pressure.

3 g (1 equivalent) of the obtained solid was dissolved in 60 mL of THF, sodium borohydride (10 equivalents) aqueous solution was slowly added thereto, and the mixture was stirred at room temperature for 3 hours. The reaction-completed solution was acidified to pH <5 with 0.3 M aqueous HCl solution, extracted with ethyl acetate, and the organic solvent was reduced under reduced pressure to obtain a compound represented by the following formula (1a) (Molecular Weight: 502.14).

[Formula 1a]

Synthetic example  2

In a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, 20.1 g (0.1 mol) of pyrene and 17.0 g (0.1 mol) of methoxybenzoyl chloride were placed in 200 g of 1,2-dichloroethane and stirred . After 15 minutes, 14.6 g (0.11 mol) of trichloroaluminum was slowly added and the reaction was carried out at room temperature for 12 hours. After completion of the reaction, trichloroaluminum was removed using water and then concentrated using an evaporator.

The resulting compound was placed in a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and 45.5 g (0.22 mol) of 1-dodecan sulfate, 16.8 g (0.3 mol) of potassium hydroxide, And the mixture was stirred at 130 DEG C for 5 hours. After completion of the reaction, the reaction product was cooled, and the reaction product was neutralized to pH 5 with 7% hydrogen chloride solution. The precipitate formed was dissolved in 300 g of methylene chloride, and the organic layer was separated. The separated organic solvent layer was concentrated by an evaporator to obtain a methyl-removed compound.

The methyl-removed compound was dissolved using 150 g of dioxane and the solution was cooled to 0 &lt; 0 &gt; C. To the cooled solution, 50 g (0.5 mol) of triethylamine was added, and then 6.1 g (0.033 mol) of cyanuric chloride was slowly added dropwise. The reaction mixture was stirred at room temperature for 2 hours, then heated to 100 DEG C and reacted for 8 hours. After completion of the reaction, the reaction product was extracted with ammonium chloride solution and ethyl acetate. The extracted solution was reduced in pressure to remove the solvent, and 160 g of tetrahydrofuran was added to the obtained compound to obtain a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction mixture was acidified with a 7% hydrogen chloride solution to a pH of less than 5, extracted with ethyl acetate and the organic solvent was reduced under reduced pressure to obtain a compound represented by the following Formula 1b (Molecular Weight: 1048.17).

[Chemical Formula 1b]

Synthesis Example 3

(30.0 g, 0.1 mol) and acetyl chloride (39.3 g, 0.5 mol) were dissolved in 1,2-dichloroethane (200 mL), and then aluminum trichloride (26.7 g, 0.2 mol) was slowly added Respectively. After the addition, the temperature was raised to 80 DEG C and the reaction was further performed for 2 hours.

After the reaction was terminated, the reaction product was slowly cooled to room temperature, and 100.0 g of distilled water was added thereto, followed by vigorous stirring. After removing the water, 100.0 g of distilled water was added again, and the same operation was repeated. The solvent was removed from the organic solvent layer using magnesium sulfate (MgSO ₄ ), and then the solvent was removed under reduced pressure. Then, the organic solvent layer was dissolved in 60.0 g of tetrahydrofuran, and slowly poured into hexane prepared in advance. The obtained solid was filtered and dried to obtain the following compound (a1).

화합물 (a1)

The compound (a1)

The resulting compound (a1) (23.1 g, 0.06 mol) was dissolved in 1,4-dioxane (200 ml) and then kept at 0 캜. Separately, a flask was prepared. Sodium hydroxide (24.0 g) and bromine (7.7 ml) were dissolved in water (100 ml), and the temperature was lowered to about 0 ° C. The mixture was slowly added to the flask containing the compound over 10 minutes. Thereafter, the mixture was stirred at room temperature for about 1 hour, and the temperature was further raised to 100 DEG C for further reaction for 2 hours.

After confirming that the reaction was terminated by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature, and an aqueous solution of HCl was added thereto, followed by extraction with 200 ml of ethyl acetate to obtain an organic layer. Next, water was removed with magnesium sulfate, the solvent was removed under reduced pressure, and the following compound (a2) was obtained by column chromatography.

화합물 (a2)

The compound (a2)

The resulting compound (a2) (19.4 g, 0.05 mol) was dissolved in dichloromethane (100 ml), thionyl chloride (10.9 ml) was added thereto, and the temperature was raised to 40 ° C and stirred for 3 hours. After completion of the reaction, the solvent was removed under reduced pressure to obtain the following compound (a3).

화합물 (a3)

The compound (a3)

The obtained compound (a3) (17.0 g, 0.04 mol) and 2-phenylindole (15.5 g) were dissolved in 1,2-dichloroethane (150 ml), and then aluminum trichloride (10.7 g) was slowly added thereto while stirring at room temperature . After the addition was completed, the temperature was raised to 80 ° C and further reacted for two hours.

After confirming that the reaction was terminated by TLC, the reaction was gradually cooled to room temperature, and 150.0 g of distilled water was added thereto. The mixture was stirred vigorously and allowed to stand. After removing the water, 150.0 g of distilled water was added again, and the same operation was repeated. The obtained organic solvent layer was washed with magnesium sulfate (MgSO ₄ ) to remove water, the solvent was then removed under reduced pressure, and the following compound (a4) was obtained by column chromatography.

화합물 (a4)

The compound (a4)

The resulting compound (a4) (11.7 g, 0.02 mol) was dissolved in tetrahydrofuran (100 ml), and lithium aluminum hydride (2.2 g) was slowly added thereto while stirring at room temperature. After completion of the reaction, the adduct was removed using a mixed solvent of water and methanol to obtain a compound represented by the following formula (1c) (Molecular Weight: 742.86).

[Chemical Formula 1c]

Synthetic example  4

20.6 g (0.1 mol) of terephthaloyl chloride, 47 g (0.2 mol) of 4-methoxypyrene and 221 g of 1,2-dichloroethane were added to a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, Prepared. 27 g (0.2 mol) of trichloroaluminum was added slowly to the solution at room temperature, then the temperature was raised to 60 ° C and the mixture was stirred for 8 hours. When the reaction was completed, the reaction solution was dropped into methanol to form a precipitate. The precipitate was filtered to obtain bis (methoxypyrylcarbonyl) benzene.

91 g (0.45 mol) of 1-dodecan sulfate, 30.3 g (0.55 mol) of potassium hydroxide and 250 g of N, N-dimethylformamide were added to the compound obtained above, followed by stirring at 120 ° C for 8 hours. After the reaction was completed, the reaction product was cooled, acidified with a 7% hydrogen chloride solution to a pH of less than 5, and the resulting precipitate was filtered to obtain a methylated compound.

The methyl-removed compound was dissolved in 150 g of dioxane, Lt; 0 &gt; C. 50 g (0.5 mol) of triethylamine was added to the cooled solution, and then 79.9 g (0.2 mol) of the intermediate B was slowly added dropwise. The reaction was heated to 100 DEG C and reacted for 8 hours. After termination of the reaction, the reaction was extracted with ammonium chloride solution and ethyl acetate. The extracted solution was then depressurized to remove the solvent. To the compound thus obtained, 160 g of tetrahydrofuran was added to obtain a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction mixture was acidified with a 7% hydrogen chloride solution to a pH of less than 5, extracted with ethyl acetate and the organic solvent was reduced to obtain a compound represented by the following Formula 1d (Molecular Weight: 1297.40).

&Lt; RTI ID = 0.0 &

Synthetic example  5

In a 250 ml two-necked flask equipped with a mechanical stirrer and a cooling tube, add 10 g (1 equivalent) of pyrene and 22 g (2 equivalents) of bromobenoyl chloride into 150 g of 1,2-dichloroethane and stir well. After 15 minutes, 14 g (2.15 eq.) Of AlCl3 was slowly added and the reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction solution was added to methanol, and the precipitated substance was filtered to remove trichloroaluminum and then dried to obtain the following compound b1.

[Formula b1]

0.5 g (1 equivalent) of 7 g (1 equivalent) of the synthesized solid, 6.9 g (2.2 equivalents) of bis (pinacolato) diboron (B2pin2), and 0.5 g of [1,1'- bis (diphenylphosphino) ferrocene] dichloropalladium 0.06 eq.) And 7.3 g (6 eq.) Of potassium acetate were dissolved in 70 mL of dioxane and placed in a 250 mL two-necked flask equipped with a mechanical stirrer and a cooling tube. This was stirred at 80 ° C for 3 hours to conduct the reaction. After completion of the reaction, the reaction product was cooled, and the product was filtered through silica gel and purified to obtain the following compound b2.

(B2)

5 g (1 equivalent) of this solid was dissolved in 100 mL of THF, sodium borohydride (10 equivalents) aqueous solution was slowly added thereto, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the solution was acidified to pH > 5 with 0.3M HCl aqueous solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain the compound represented by Formula 1e (Molecular Weight: 666.43).

[Formula 1e]

Synthetic example  6

After dissolving methoxy pyrene (23.2 g, 0.1 mol) and acetyl chloride (39.3 g, 0.5 mol) in 1,2-dichloroethane (200 mL), aluminum trichloride (26.7 g, 0.2 mol) was slowly Respectively. After the addition was completed, the temperature was raised to 80 DEG C and further reacted for 2 hours.

After the reaction was terminated, the reaction product was slowly cooled to room temperature, and 100.0 g of distilled water was added thereto, followed by vigorous stirring. After removing the water, 100.0 g of distilled water was added again, and the same operation was repeated. The solvent was removed from the organic solvent layer using magnesium sulfate (MgSO 4), and then the solvent was removed under reduced pressure. Then, the organic solvent layer was dissolved in 60.0 g of tetrahydrofuran, and slowly poured into hexanes prepared in advance. The obtained solid was filtered and dried to obtain the following compound (c1).

화합물 (c1)

The compound (c1)

The obtained compound (c1) (15.8 g, 0.05 mol) and 4-bromophenylhydrazine hydrochloride (24.6 g, 0.11 mol) were dissolved in 300 ml of ethanol and the temperature was raised to 80 ° C and the mixture was stirred for 5 hours.

After the reaction was completed, the temperature was lowered to room temperature, and then the reactant was slowly poured into 600.0 g of distilled water. The obtained solid was filtered and washed with 50 ml of ethyl acetate to obtain the following compound (c2).

화합물 (c2)

The compound (c2)

The resulting compound (c2) (18.6 g, 0.03 mol), 2-bromo-6-methoxynaphthalene (15.6 g), bis (triphenylphosphine) palladium (11) dichloride (6.3 g), and CuI triethylamine) and tetrahydrofuran (1: 4, 200 ml), and the mixture was heated to 70 ° C and stirred for 12 hours.

After the reaction was terminated, the temperature was lowered to room temperature and the reaction was slowly poured into 1000.0 g of cold distilled water. The obtained solid was filtered, and then the following compound (c3) was obtained through column chromatography.

화합물 (c3)

The compound (c3)

The obtained compound (c3) (11.6 g, 0.02 mol), 1-dodecanethiol (15.2 g) and sodium hydroxide (3.0 g) were dissolved in dimethylacetamide (200 ml) Lt; / RTI &gt;

After confirming that the reaction was terminated by TLC, the temperature was lowered to room temperature, and then the reactant was slowly poured into 700.0 g of cold distilled water to form a solid. The resulting solid was filtered, dissolved in 100 ml of tetrahydrofuran, and poured into 500 ml of hexane. The solid in the solution was filtered to obtain a compound represented by the following formula (1f) (Molecular Weight: 732.84).

(1f)

Synthetic example  7

Step 1 : Fried - Craft Acylation ( Friedel -Craft Acylation ) reaction

To the flask was added a solution of 50.0 g (0.23 mol) of pyrene, 194.4 g (0.53 mol) of 4-bis-4-methoxyphenyl-methylbenzoyl chloride and 818 g of 1,2-dichloroethane. Subsequently, 70.6 g (0.53 mol) of aluminum chloride was added slowly to the solution at room temperature, and the temperature was raised to 60 DEG C and the mixture was stirred for 8 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered and dried.

Step 2 : Methyl group removal ( demethylation ) reaction

(0.06 mol) of the compound synthesized in the first step, 12.1 g (0.06 mol) of 1-dodecan sulfate, 3.9 g (0.07 mol) of potassium hydroxide and 165 g of N, N-dimethylformamide were added to the flask Followed by stirring at 120 DEG C for 8 hours. The mixture was then cooled and neutralized to pH 7 with 10% hydrogen chloride solution. The precipitate formed was extracted with ethyl acetate and dried.

Step 3 : Reduction reaction

30.0 g (0.04 mol) of the compound synthesized in the second step and 230 g of tetrahydrofuran were added to the flask to prepare a solution. Subsequently, 15.1 g (0.4 mol) of sodium borohydride aqueous solution was slowly added to the solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to pH 7 with 10% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula 1g (Molecular Weight: 810.95).

[Formula 1g]

Synthetic example  8

Step 1 : Fried - Craft Acylation ( Friedel -Craft Acylation ) reaction

To the flask, 10 g (0.0494 mol) of pyrene, 8.43 g (0.0494 mol) of 4-methoxybenzoyl chloride and 100.11 g of 1,2-dichloroethane were added to prepare a solution. Subsequently, 6.59 g (0.0494 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 2 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered and dried.

Then, 15.46 g (0.0460 mol) of the compound obtained above, 4.07 g (0.0153 mol) of 1,3,5-benzenetricarboxylic acid chloride and 102.62 g of 1,2-dichloroethane were added to the flask to prepare a solution. Subsequently, 6.13 g (0.0460 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 6 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered and dried.

Step 2 : Methyl group removal ( demethylation ) reaction

15.17 g (0.0130 mol) of the compound obtained above, 13.18 g (0.0651 mol) of 1-dodecan sulfate, 4.38 g (0.0781 mol) of potassium hydroxide and 76.37 g of N, N-dimethylformamide were added to the flask, And stirred for 3 hours. The mixture was then cooled, neutralized to about pH 6-7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried.

Step 3 : Reduction reaction

11.84 g (0.0105 mol) of the compound obtained above and 40 g of tetrahydrofuran were added to the flask to prepare a solution. Then, an aqueous solution of 7.98 g (0.2108 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula 1h (Molecular Weight: 1135.28).

[Chemical Formula 1h]

Cross-linking agent  synthesis

Synthetic example  9

Triphenylamine (5 g, 20.38 mmol) was dissolved in dimethylformamide (DMF) (30 g) and N-bromosuccinimide (11.97 g, 67.23 mmol) was added to the flask. After the dropwise addition, the mixture is stirred at room temperature for 12 hours. After extraction with dichloromethane (DCM) to remove the solvent, the product was separated by column chromatography to obtain the following compound S1.

[Compound S1]

The above compound S1 (0.5 g, 1.04 mmol) was dissolved in tetrahydrofuran (THF) (5 mL) and then n-BuLi 1.6 M in hexane (2.3 mL, 3.64 mmol) was slowly added dropwise to the flask at -78 ° C . Bromomethyl methyl ether (0.65 g, 5.2 mmol) was then added dropwise thereto, and the mixture was slowly heated and stirred for 1 hour and 30 minutes. The reaction mixture was quenched with NH ₄ Cl solution, extracted with EtOAc, and then the solvent was removed. The product was isolated by column chromatography to obtain a compound represented by the following formula (2a).

(2a)

Synthetic example  10

(3g, 8.27mmol) was dissolved in DMF (30g), and then NaH 60% in mineral &lt; RTI ID = 0.0 &gt; After dropwise addition of oil (0.83 g, 20.75 mmol) at 0 占 폚, MeI (2.93 g, 20.64 mmol) was further added dropwise. After stirring for 12 h at room temperature, NH ₄ Cl solution was added, extracted with EtOAc and the solvent was removed. The product was separated by column chromatography to obtain a compound represented by the following formula (2b).

(2b)

(화학식 2b에서 Me는 메틸기임)

(Me in the formula (2b) is a methyl group)

Synthesis Example 11

After dissolving 1,1'-Oxybis [4-methoxy-benzene] (3 g, 13.02 mmol) in DCM (50 mL), AlCl ₃ (8 g, 60 mmol) was added dropwise at 0 ° C. Acetyl chloride (4.71 g, 60 mmol) was then added dropwise, followed by stirring at room temperature for 12 hours. The HCl solution was added and extracted with DCM to remove the solvent. The product was purified by column chromatography to give the following compound k.

[화합물 k]

[Compound k]

Lithium aluminum hydride (1.138 g, 30 mmol) was added dropwise at 0 ° C to the above compound k (3 g, 7.52 mmol) in anhydrous THF (50 g), and the mixture was stirred at room temperature for 2 hours Respectively. 6N NaOH was added and extracted with EtOAc and the solvent was removed. The product was purified by column chromatography to obtain a compound represented by the following formula (2c).

[Chemical Formula 2c]

Polymerization Example

Polymerization Example  One

The flask was charged with 1H-inodole (11.7 g, 0.1 mol), 6-hydroxyphenanthrene-1-carbaldehyde (22.2 g, 0.1 mol), p-toluenesulfonic acid monohydrate (pTSA, 9.5 g, 60 g) was added thereto, followed by stirring at 100 占 폚. Samples were taken from the polymerization reactants at intervals of 1 hour and the reaction was completed when the weight average molecular weight of the sample was 3,100. After completion of the reaction, 100 g of distilled water was added to extract the pTSA which was used as a catalyst. After stirring and standing, the supernatant was removed, methanol was added to precipitate the precipitate, and the remaining monomer was removed using methanol to obtain To obtain a polymer (Mw: 3,500) containing structural units.

[Chemical Formula 3]

Polymerization Example  2

To the flask was added 1,2,3,4-tetrahydroquinoline (13.3 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, g) was added thereto, followed by stirring at 100 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 3,300. After completion of the reaction, 100 g of distilled water was added to remove the pTSA used as a catalyst. After stirring, the supernatant was removed, and methanol was added to precipitate the precipitate. The remaining monomer was removed using methanol to obtain To obtain a polymer (Mw: 3,700) containing structural units.

(3b)

Polymerization Example  3

To the flask was added Thianaphthene (13.4 g, 0.1 mol), 9-Fluorenone (18 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxane Lt; / RTI &gt; Samples were taken from the polymerization reactants at intervals of 1 hour and the reaction was completed when the weight average molecular weight of the sample was 2,900. After completion of the reaction, 100 g of distilled water was added to remove the pTSA used as a catalyst. After stirring and standing, the supernatant was removed, methanol was added to precipitate the precipitate, and the remaining monomer was removed using methanol to obtain To obtain a polymer (Mw: 3,200) containing structural units.

[Chemical Formula 3c]

Polymerization Example  4

To the flask was added 9 (10H) -Acridanone (19.5 g, 0.1 mol), Benzophenone (18.2 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxane And then stirred at 100 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,300. After completion of the reaction, 100 g of distilled water was added to extract the pTSA used as a catalyst, and after stirring, the supernatant was removed, and the precipitate formed by adding methanol was removed by filtration. The remaining monomer was removed by using methanol, To obtain a polymer (Mw: 2,800) containing structural units.

(3d)

Polymerization Example  5

After adding 9H-carbazole (16.7 g, 0.15 mol), Anthrone (17.5 g, 0.09 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxane (152 g) Lt; 0 &gt; C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 3,500. After completion of the reaction, 100 g of distilled water was added to extract the pTSA used as a catalyst. After stirring and standing, the supernatant was removed. Methanol was added to remove the precipitate, and the remaining monomer was removed using methanol to obtain To obtain a polymer (Mw: 3,800) containing structural units.

[Formula 3e]

Polymerization Example  6

(5.8 g, 0.05 mol), 6,6 '- (9H-fluorene-9,9-diyl) dinaphthalen-2-ol (22.5 g, 0.05 mol), perylene-3-carbaldehyde , 0.1 mol), p-toluenesulfonic acid monohydrate (pTSA, 9.5 g, 0.05 mol) and 1,4-dioxane (60 g) were added and stirred at 100 ° C. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 2,200. After completion of the reaction, 100 g of distilled water was added to extract the pTSA used as a catalyst. After stirring and standing, the supernatant was removed, and methanol was added to precipitate the precipitate. The remaining monomer was removed using methanol to obtain To obtain a polymer (Mw: 2,600) containing structural units.

(3f)

Polymerization Example  7

450.5 g (1.0 mol) of 9,9'-bishydroxynaphthylfluorene and 3.1 g (0.02 mol) of diethyl sulfate were placed in 250 g of propylene glycol monomethyl ether acetate (PGMEA), and while maintaining the temperature of the reactor at 100 ° C. And sufficiently dissolved by stirring.

After about 10 minutes, 166.4 g (1.0 mol) of 1,4-bismethoxymethylbenzene was added dropwise, and the temperature was raised to 120 占 폚 and polymerization was carried out for 14 hours.

Thereafter, molecular weight measurement and purification were carried out at intervals of 1 hour to obtain a polymer containing a structural unit represented by the following formula (3g). The weight average molecular weight of the obtained polymer was 1,800 and the degree of dispersion was 1.41.

[Formula 3g]

Polymerization Example  8

65.48 g (0.3 mol) of 1-hydroxypyrrole and 103.12 g (1.0 mol) of 9,9'-bisphenolfulrene were placed in 270.34 g of propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution. Then, 4.62 g (0.05 mol) of diethyl sulfate was added to the solution, 199.48 g (2.0 mol) of 1,4-bismethoxymethylbenzene was added dropwise thereto, and the temperature was raised to 130 ° C. to carry out a polymerization reaction for 21 hours.

Then, molecular weight measurement and purification were carried out at intervals of 1 hour in the same manner as in Synthesis Example 1 to obtain a polymer containing a structural unit represented by the following formula (3h). The weight average molecular weight of the obtained polymer was 2,100 and the degree of dispersion was 1.68.

[Chemical Formula 3h]

Manufacture of thin films

Example  1 to 26, Comparative Example  1 to 6

Solids in the composition as shown in Table 1 were dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL ratio: 1: 1, volume ratio) A composition was prepared.

  Monomer polymer Cross-linking agent additive Weight ratio of polymer: monomer Example 1 Formula 1a Formula 3a Formula 2a 4b 30:70 Example 2 1b 3b 2b Formula 4c 30:70 Example 3 Formula 1c Formula 3a 2b 4a 30:70 Example 4 3b Formula 2c 4a 30:70 Example 5 1d Formula 3c Formula 2a 4b 30:70 Example 6 (3d) 2b 4b 30:70 Example 7 1e Formula 3a Formula 2c 4b 30:70 Example 8 3b 2b Formula 4c 30:70 Example 9 1f 3e 2b Formula 4c 30:70 Example 10 Formula 3f Formula 2c 4a 30:70 Example 11 1 g 3b Formula 2a 4a 30:70 Example 12 3e 2b 4a 30:70 Example 13 1h 3b 2b 4a 30:70 Example 14 Formula 1a 3g Formula 2a 4a 70:30 Example 15 1b 2b 4a 60:40 Example 16 Formula 1c Formula 2a 4a 60:40 Example 17 1d Formula 2c Formula 4c 70:30 Example 18 1e Formula 2c Formula 4c 60:40 Example 19 1f Formula 2a Formula 4c 70:30 Example 20 1 g Formula 2a Formula 4c 50:50 Example 21 Formula 1a 3h Formula 2c 4b 50:50 Example 22 Formula 1c 2b 4b 60:40 Example 23 1e 2b 4b 60:40 Example 24 1f Formula 2c 4b 60:40 Example 25 1 g Formula 2c 4b 70:30 Example 26 1h Formula 2a 4b 70:30 Comparative Example 1 Formula 1c - - 100: 0 Comparative Example 2 1d - - 100: 0 Comparative Example 3 1f - - 100: 0 Comparative Example 4 - Formula 3a 0: 100 Comparative Example 5 Formula 1a - 100: 0 Comparative Example 6 Formula 1a - Formula 1 4a 100: 0

4a, 4b, and 4c of the additive in Table 1 are expressed as follows.

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

In Table 1, the content of the crosslinking agent is 5 wt% based on 100 wt% of the entire hard mask composition, and the content of the additives is 0.05 wt% based on 100 wt% of the entire hard mask composition.

Evaluation 1: Thin film Awareness of corrosion

The hard mask composition according to Examples 1-3, 5, 6, 10, 11, 14-16, 18, 19, 23, and 24 and the hard mask composition according to Comparative Examples 2, 3, And the film was heat-treated on a hot plate at 350 for 2 minutes to form a thin film, and then the thickness of the thin film was measured. Subsequently, the thin film was dry etched using a mixed gas of CHF ₃ / CF _{4, and} the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation.

[Equation 1]

Etching rate (Å / s) = (initial thin film thickness - thin film thickness after etching) / etching time

The results are shown in Table 2.

Bulk etch rate (Å / sec) Example 1 27 Example 2 28 Example 3 26 Example 5 27 Example 6 25 Example 10 26 Example 11 26 Example 14 27 Example 15 28 Example 16 26 Example 18 27 Example 19 25 Example 23 26 Example 24 26 Comparative Example 2 30 Comparative Example 3 29 Comparative Example 6 29

Referring to Table 2, the hard mask thin film according to Examples 1-3, 5, 6, 10, 11, 14-16, 18, 19, 23, and 24 prepared by blending the polymer and the monomer as the material of the hard mask layer Of the hard mask thin films according to Comparative Examples 2, 3, and 6 prepared using only the monomers.

Evaluation 2: Gap-fill characteristics and planarization characteristics of thin films

A silicon oxide (SiO _x ) layer having a thickness of 3000 Å was formed on a silicon wafer by a chemical vapor deposition (CVD) method. Subsequently, the hard mask composition according to Examples 1, 4, 6, 9, 12-15, 17, 19, 22, 25, 26 and Comparative Examples 1, 2, 4, 5 was applied on the silicon oxide film by spin coating And then heat-treated at 350 DEG C for 2 minutes to form a hard mask layer.

Subsequently, a silicon nitride (SiN _x ) layer was formed on the hard mask layer by chemical vapor deposition. Subsequently, the photoresist for KrF was spin-coated and heat-treated at 110 ° C. for 60 seconds, and then exposed using ASML (XT: 1400, NA 0.93) exposure equipment and developed with tetramethylammonium hydroxide (2.38 wt % TMAH aqueous solution).

Subsequently, silicon nitride (SiN _x ) layer was dry-etched using CHF ₃ / CF ₄ mixed gas plasma using the patterned photoresist as a mask. Then Example 1, 4, 6, 9, 12-15, 17, 19, 22, 25 by using the silicon nitride (SiN _x) layer patterned by the above process as a mask, using the N ₂ / O ₂ mixed gas plasma , 26 and Comparative Examples 1, 2, 4, 5 were dry-etched. A cross section of the hard mask pattern was observed using a scanning electron microscope (SEM). The results are shown in Table 3.

Hard mask pattern Example 1 Vertical shape Example 4 Vertical shape Example 6 Vertical shape Example 9 Vertical shape Example 12 Vertical shape Example 13 Vertical shape Example 14 Vertical shape Example 15 Vertical shape Example 17 Vertical shape Example 19 Vertical shape Example 22 Vertical shape Example 25 Vertical shape Example 26 Vertical shape Comparative Example 1 Tapered shape
(Taperd Shape) Comparative Example 2 Pattern collapse Comparative Example 4 Tapered shape Comparative Example 5 Pattern collapse

Referring to Table 3, the hard mask layers formed from the hard mask composition according to Examples 1, 4, 6, 9, 12-15, 17, 19, 22, 25, and 26 were all patterned in a vertical shape, The hard mask layer formed from the hard mask composition according to 1, 2, 4, and 5 may not be patterned in a vertical shape, and may be patterned in a tapered shape in which the cross section is narrowed toward the upper end of the patterning, As shown in Fig.

Evaluation 3: Gap-fill and planarization characteristics

The patterned wafers were coated with the hard mask compositions according to Examples 1, 3, 7, 9, 10, 14, 16-18, 20-23 and Comparative Examples 1 to 5 and baked at 100 to 200 DEG C for 10 to 100 seconds After washing the part of the resin with PGMEA, the resin was applied again and then baked at 350 ° C for 2 minutes. Then, gap-fill characteristics were observed using V-SEM equipment.

The cross section of the pattern was observed with a scanning electron microscope (SEM), and gap-fill characteristics were determined as to whether voids were generated.

The planarization characteristics were confirmed as step 1 and step 2.

10, the 'step 1' refers to the difference between the thin film thickness h1 measured at the non-pattern portion between the pattern and the pattern and the thin film thickness h2 formed at the pattern portion in the patterned wafer . In this case, the h1 value is an average value of a plurality of portions of the pattern portion and the non-pattern portion, and the h2 value is an average thickness of the thin film formed at the pattern portion.

Referring to FIG. 11, the 'step 2' is a diagram showing the relation between the thin film thickness h1 measured at the non-pattern portion between the pattern and the pattern and the edge of the patterned wafer (here, from the end of the wafer to one micrometer Quot; edge &quot;) of the thin film thickness h3. Here, 'step 2' is also referred to as a built-in step difference. On the other hand, in the measurement of the step 2, the h1 is measured at the portion closest to the edge.

The smaller the steps 1 and 2, the better the planarization characteristic.

The results of the gap-fill characteristic and the planarization characteristic are shown in Table 4 below.

Gap fill characteristics (with or without void) Level 1 (nm) Step 2 (nm) Example 1 void None 28 21 Example 3 void None 30 24 Example 7 void None 29 22 Example 9 void None 35 27 Example 10 void None 37 31 Example 14 void None 28 22 Example 16 void None 31 25 Example 17 void None 27 22 Example 18 void None 30 23 Example 20 void None 29 22 Example 21 void None 28 22 Example 22 void None 35 28 Example 23 void None 37 30 Comparative Example 1 void 65 52 Comparative Example 2 void 77 62 Comparative Example 3 void 59 46 Comparative Example 4 Void 65 51 Comparative Example 5 void None 77 60

Referring to Table 4, the thin film formed from the hard mask composition according to Examples 1, 3, 7, 9, 10, 14, 16-18, 20-23 had void- It can be seen that the thin film formed from the hard mask composition according to Comparative Examples 1 to 4 has voids observed in the patterned wafer.

In addition, the thin films formed from the hard mask compositions according to Examples 1, 3, 7, 9, 10, 14, 16-18, 20-23 had a step value It is understood that the planarization characteristic is excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

100: film structure 110: substrate
120: organic layer 130: silicon-containing thin film layer
140: antireflection layer 150: photoresist layer

Claims (23)

(S1) forming a first organic layer by applying a first composition on a substrate having a plurality of patterns and curing the first composition;
Applying a liquid material to the first organic layer to remove a portion of the first organic layer (S2); And
(S3) forming a second organic layer by applying a second composition on the first organic layer,
Lt; / RTI &gt;
Wherein the first composition and the second composition each independently comprise a polymer comprising a structural unit represented by the following formula 1, a cyclic group having a molecular weight of 1,500 or less and a benzene ring fused with at least three substituted or unsubstituted benzene rings in the structure Monomers, and solvents
Membrane Structure Manufacturing Method:
[Chemical Formula 1]

In Formula 1,
A ¹ is a divalent cyclic group containing at least one substituted or unsubstituted benzene ring,
B ¹ is a divalent organic group,
* Is the connection point. The method of claim 1,
Wherein the first organic layer partially removed is left in the gap of the pattern. The method of claim 1,
The liquid substance may be at least one selected from the group consisting of? -Butyrolactone,? -Valerolactone, ethyl lactate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether acetate,? -Hydroxy? Butylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, Ethylene glycol monomethyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, poly (ethylene glycol), propylene glycol Glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate Propyleneglycol monomethyl ether propionate, ethyleneglycol diacetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, formamide, monomethyl formate Amide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, N-methylpyrrolidone, methoxymethylpropionate, methoxyethylpropionate, Ethoxyethyl propionate, ethoxypropyl propionate, ethoxybutyl propionate, dimethyl sulfone, dimethyl sulfoxide, sulfonic acid, isopropoxy propionate, methoxy propionate, ethoxy methyl propionate, ethoxy ethyl propionate, Acetone, acetyl acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. The method for manufacturing a membrane structure. The method of claim 1,
Wherein the liquid material is applied in a content ranging from 0.1 cc to 100 cc. The method of claim 1,
Wherein the first organic layer and the second organic layer are hard mask layers. The method of claim 5,
Wherein the second organic layer is formed directly over the first organic layer from which a portion is removed. The method of claim 1,
Wherein the monomers each independently comprise a monovalent to trivalent cyclic group derived from a substituted or unsubstituted cyclic group selected from the following Group 1:
[Group 1]

In the group 1,
Z ¹ represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof. The method of claim 1,
Wherein the molecular weight of the monomer is 500 or more and 1,300 or less. The method of claim 1,
Wherein the monomer comprises a ring group fused with at least four substituted or unsubstituted benzene rings. The method of claim 1,
Wherein the monomer is represented by any one of the following formulas (1-1) to (1-6):
[Formula 1-1]

In Formula 1-1,
A is a substituted or unsubstituted aromatic ring group,
X ¹ , X ² and X ³ are each independently a monovalent group derived from substituted or unsubstituted indole,
Y ¹ , Y ² and Y ³ are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C20 alkyl An amino group, or a substituted or unsubstituted C1 to C30 alkoxy group,
m ¹ , m ² , m ³ , n ¹ , n ² and n ³ are each independently 0 or 1.
However, m ^1, m ² and m ^3, at least one is 1, and when m ¹ is 0, n ¹ is 0, when m ² is 0 and n ² is 0, m ³ is 0, n ³ is 0:
[Formula 1-2]

In Formula 1-2,
T is a triazine or triazine derivative,
R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.
Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group:
[Formula 1-3]

In Formula 1-3,
A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
k and l are each independently 0 or 1, satisfying 1? k + 1? 2,
m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,
p and q are each independently an integer of 1 or more and satisfy 1? p + q? (the maximum number of substituents that A0 can have)
[Formula 1-4]

In Formula 1-4,
A ¹ is An aliphatic cyclic group or an aromatic cyclic group,
A ² To A &lt; ⁴ &gt; each represent a benzene group,
X ¹ to X ³ each independently represent a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Or a substituted or unsubstituted C1 to C30 alkoxy group,
M is CR ^a , SiR ^b , N, P, PR ^c R ^d or PR ^e ,
n is an integer of 1 to 4,
Wherein R ^a , R ^b , R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
R ^e is oxygen (O) or sulfur (S):
[Formula 1-5]

In Formula 1-5,
A ¹ to A ³ each independently represents an aliphatic cyclic group or an aromatic cyclic group,
X ¹ to X ³ each independently represent a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,
n is an integer from 3 to 5,
m is an integer from 1 to 3;
[Chemical Formula 1-6]

In the above formulas 1-6,
A ⁰ and A ¹ are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,
X is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,
L ⁰ is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
Y is a boron (B) -containing group,
n is an integer of 1 to 5; The method of claim 1,
A ¹ in the formula 1 is at least two divalent ring structure resulting film production method comprising a ring in its structure. The method of claim 1,
A ¹ in the formula 1 are listed in the Group 2 and 3 substituted or unsubstituted method of any of the ring moieties single film structure forming:
[Group 2]

In the group 2,
M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl:
[Group 3]

In the group 3,
R ⁰ and R ¹ are each independently selected from the group consisting of hydrogen, a hydroxyl group, a methoxy group, an ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, It is a combination. The method of claim 1,
Wherein B ¹ in the formula ( ¹⁾ is represented by the following formula (3):
(3)

In Formula 3,
a and b are each independently an integer of 0 to 2,
L is any one of the substituted or unsubstituted moieties listed in Group 2 below, or any of the groups listed in Group 4 below.
[Group 2]

In the group 2,
M is a substituted or unsubstituted C1 to C5 alkylene group, -O-, -S-, -SO ₂ - a, or a carbonyl:
[Group 4]

In Group 4 above,
X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide-containing group, or a combination thereof,
Y ¹ and Y ² are each independently hydrogen, a hydroxy group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, or at least one of the combinations thereof are Y ¹ and Y ² is a substituted or An unsubstituted C6 to C30 aryl group,
Z ⁷ to Z ¹⁰ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a halogen group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group , A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
g, h, i and j are each independently an integer of 0 to 2,
k is an integer of 1 to 3,
"*" Is the connection point. The method of claim 13,
In the group 4, X ¹ and X ² are each independently a substituted or unsubstituted C6 to C50 arylene group, and the C6 to C50 arylene group is any one of the moieties listed in the following group 5:
[Group 5]

The method of claim 1,
Wherein the polymer comprises two or more different structural units represented by the general formula (1). The method of claim 1,
Wherein the curing process after applying the second composition proceeds at a higher temperature than the curing process after applying the first composition. The method of claim 1,
Wherein the first composition and the second composition each independently comprise a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), a photoacid generator (PAG), or a combination thereof. 17. The method of claim 16,
The crosslinking agent may be selected from the group consisting of methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, Methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination of these. The method of claim 1,
The solvent contained in the first composition and the solvent included in the second composition are each independently selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) Propyleneglycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone Methylpyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, or a combination thereof. The method of claim 1,
Wherein the first composition and the second composition are each independently applied in a thickness of 300 A to 10 [mu] m. The method of claim 1,
Wherein one side of the substrate includes a first portion having a plurality of patterns and a second portion having no pattern and the second organic layer step sum (S3) is smaller than the first organic layer step sum (S1) &Lt; / RTI &gt; 21. A process for producing a film structure, comprising: preparing a film structure produced according to any one of claims 1 to 21;
Forming a silicon-containing thin film layer on the film structure;
Forming a photoresist layer on the silicon-containing thin film layer;
Exposing and developing the photoresist layer to form a photoresist pattern; And
Selectively removing the silicon-containing thin film layer and the first organic layer, the second organic layer, or a combination thereof in the film structure using the photoresist pattern
&Lt; / RTI &gt; The method of claim 22,
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.

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