KR20190081973A - Compound, organic layer composition, and method of forming patterns - Google Patents

Abstract

The present invention relates to a moiety represented by chemical formula 1, a compound having a dendrimer structure including a moiety having a fluorene structure, an organic layer composition comprising the compound and a method for forming patterns using the organic layer composition. The chemical formula 1 is the same as defined in the specification. The compound of the present invention has excellent thermal resistance and etching resistance while having solubility.

Description

TECHNICAL FIELD [0001] The present invention relates to a compound, an organic film composition,

A novel compound, an organic film composition comprising the compound, and a pattern forming method using the organic film composition.

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 serves as an intermediate film for transferring 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.

Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. The spin-on coating method is not only easy to process but also can improve gap-fill and planarization properties. In order to realize a fine pattern, it is necessary to form multiple patterns. In this case, the embedding characteristic of embedding the pattern in the film without voids is required. Further, in the case where there is a step on the substrate to be processed, or in the case where a pattern dense portion and an area having no pattern exist together on the wafer, it is necessary to planarize the film surface by the underlayer film.

There is a demand for an organic film material which can satisfy the properties required for the hard mask layer described above.

One embodiment provides a novel compound having excellent heat resistance and corrosion resistance while securing solubility.

Another embodiment provides an organic film composition comprising such a compound.

Another embodiment provides a method of forming a pattern using the organic film composition.

According to one embodiment, there is provided a compound having a dendrimer structure including a moiety represented by the following formula (1) and a moiety including a fluorene structure.

[Chemical Formula 1]

In Formula 1,

X is a substituted or unsubstituted C6 to C50 aromatic ring group,

Y is a group represented by the following formula 2:

(2)

In Formula 2,

R ¹ and R ² are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

n is an integer from 0 to 5,

* Is the connection point.

In Formula 1, X may be either a substituted or unsubstituted ring group listed in Group 1 below.

[Group 1]

In the group 1,

Ra represents a direct bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group , A substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

The compound may be represented by any one of the following formulas (3) to (5)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,

A is a moiety represented by the above formula (1)

B is a moiety comprising a fluorene structure,

로 표현되는 모이어티로서, 여기서 A 및 B는 상기에서 정의한 바와 같고 *는 연결지점이고,D is

Wherein A and B are as defined above and * is a connection point,

a to t are independently 0 or 1, at least one of a to d in the formulas (3) to (5) is 1, at least one of e to h in the formulas (4) and (5) is 1, At least one of t is 1.

The moiety containing the fluorene structure may be any of a substituted or unsubstituted ring group selected from the group 2 below.

[Group 2]

The weight average molecular weight of the compound may be 500 to 200,000.

According to another embodiment, there is provided an organic film composition comprising the above-described compound, and a solvent.

The compound may be contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the organic film composition.

According to another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: forming a material layer on a substrate; applying an organic film composition comprising the polymer and the solvent on the material layer; heat treating the organic film composition to form a hard mask layer Containing thin film layer on the hard mask layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the silicon-containing thin film layer and the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the organic film composition may be performed by a spin-on coating method.

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

A compound according to one embodiment has a dendrimer structure and has a number of functional groups. As a result, the intermolecular interaction is increased while ensuring basic corrosion resistance, and the gap-fill and planarization characteristics are excellent.

FIG. 1 is a flow chart for explaining a pattern forming method according to an embodiment,
2 is a reference diagram for explaining calculation formula 1 for calculating a step sum,
3 is a reference diagram for explaining the calculation formula 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.

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 carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkenyl group, a C2 to C30 alkenyl group, A C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, C6 to C15 cycloalkynyl groups, C3 to C30 heterocycloalkyl groups, and combinations thereof.

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

Also, unless otherwise defined herein, '*' refers to the point of attachment of a compound or moiety.

The compounds according to one embodiment are described below.

A compound according to one embodiment comprises a moiety represented by the following formula (1), and a moiety comprising a fluorene structure.

[Chemical Formula 1]

In Formula 1,

X is a substituted or unsubstituted C6 to C50 aromatic ring group,

Y is a group represented by the following formula 2:

(2)

In Formula 2,

R ¹ and R ² are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

n is an integer from 0 to 5,

* Is the connection point.

In the compound, moieties represented by Formula 1 and moieties including a fluorene structure are located at an intersecting position to form a dendrimer structure.

Dendrimer is a macromolecule with a regular branch structure, which is synthesized by connecting the constituent units one at a time. The stereostructure of the dendrimer has spherical shape, rugby shape, and cone shape depending on the structure of the central unit, and it can be made from several nanometers to tens nanometers.

Compounds according to one embodiment have such a dendrimer structure that they have a large number of functional groups in the structure, thereby increasing intermolecular interactions, thereby further enhancing the gap-fill and planarization characteristics. Further, the compound has an aromatic ring group in its structure, and thus has excellent basic corrosion resistance and heat resistance.

The compound has a dendrimer structure extending in four chambers, and in the formula (1), the Y moiety becomes a binding site connected to a moiety having the fluorene structure. The moiety represented by the formula (1) is connected to four binding sites (Y) represented by the formula (2), and a substituted or unsubstituted C6 to C50 aromatic ring group (Y) is located at the center.

In Formula 1, X may be any of a substituted or unsubstituted ring group listed in Group 1 below, but is not limited thereto.

[Group 1]

In the group 1,

R ^a is a direct bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

It is a matter of course that the positions of the four binding sites connected to the fluorene moiety in Formula 1 are not particularly limited.

The cyclic groups in Group 1 may be unsubstituted as shown, but may be substituted by, for example, a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group , Or a combination thereof.

Y in the formula (1) is represented by the formula (2), and in the formula (2), for example, n = 1 and R ¹ and R ² may be hydrogen, but are not limited thereto.

For example, the compound may be represented by the following formula (3).

(3)

In Formula 3,

A is a moiety represented by the above formula (1)

B is a moiety comprising a fluorene structure,

a to d are each independently 0 or 1, and at least one of a to d is 1;

For example, the compound may be represented by the following formula (4).

[Chemical Formula 4]

In Formula 4,

A is a moiety represented by the above formula (1)

B is a moiety comprising a fluorene structure,

a to h each independently represents 0 or 1, provided that at least one of a to d is 1 and at least one of e to h is 1;

The formula (4) represents a structure in which the unit structure is further extended from the structure of the formula (3).

For example, the compound may be represented by the following formula (5).

[Chemical Formula 5]

In Formula 5,

A is a moiety represented by the above formula (1)

B is a moiety comprising a fluorene structure,

로 표현되는 모이어티로서, 여기서 A 및 B는 상기에서 정의한 바와 같고 *는 연결지점이고,D is

Wherein A and B are as defined above and * is a connection point,

each of a to t is independently 0 or 1, at least one of a to d is 1, at least one of e to h is 1, and at least one of i to t is 1.

The formula (5) represents a structure in which the unit structure is further extended from the structure of the formula (4). However, it is needless to say that the above-mentioned compounds can also include the dendrimer structure further extended in the following formula (5).

The moiety having a fluorene structure in Formula 1 may be any of a substituted or unsubstituted ring group selected from the following Group 2, but is not limited thereto.

[Group 2]

The moieties of Group 2 may be unsubstituted as shown, but may be substituted by, for example, a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, And may be substituted by a combination of these.

The compound may have a weight average molecular weight of about 500 to 200,000, and more specifically, a weight average molecular weight of about 1,000 to 20,000. 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 compound and the solubility in solvents.

When the above compound is used as an organic film material, it is possible to form a uniform thin film without forming pin-holes and voids or deteriorate thickness scattering in the baking process, or when a step is present in the lower substrate (or film) It is possible to provide excellent gap-fill and planarization characteristics.

According to another embodiment, there is provided an organic film composition comprising the above-described compound, and a solvent.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the compound. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) But are not limited to, methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, , Methyl pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.

The compound may be included in an amount of about 0.1 to 50% by weight, about 0.1 to 30% by weight, or about 0.1 to 15% by weight based on the total amount of the organic film composition. By including the compound in the above range, the thickness, surface roughness and planarization degree of the organic film can be controlled.

The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

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

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 Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can be used.

As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking forming substituent group having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.

The acid generator may be an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.

According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be in the form of a hardened layer, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc., and an organic thin film used for electronic devices, .

Hereinafter, a method of forming a pattern using the above-described organic film composition will be described with reference to FIG.

1 is a flowchart illustrating a pattern forming method according to an embodiment.

The pattern forming method according to one embodiment includes the steps of forming a material layer on a substrate (S1), applying (S2) an organic film composition including the above-mentioned polymer and a solvent on the material layer, Forming a hard mask layer (S3) on the hard mask layer, forming a silicon-containing thin film layer on the hard mask layer (S4), forming a photoresist layer on the silicon-containing thin film layer (S5) (S6) selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a part of the material layer using the photoresist pattern, And etching the exposed portion of the material layer (S8).

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

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.

The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but can be applied, for example, to a thickness of about 50 to 200,000 angstroms.

The step of heat-treating the organic film composition may be performed at, for example, about 100 to 700 DEG C for about 10 seconds to 1 hour.

The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.

Further, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer before the step of forming the photoresist layer.

The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, a heat treatment process may be performed at about 100 to 700 ° C after exposure.

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof.

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

20 g (0.044 moles) of bis-9,9-naphtholfluorene was dissolved in DMF together with potassium carbonate and methyl iodide, methylated with -OH and placed in tetrahydrofuran (180 g) in a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube The temperature was lowered to -78 deg. C and dissolved by stirring for 3 hours. 6.2 g (0.097 mol) of n-butyllithium was slowly added thereto, followed by stirring for 1 hour. 5 g (0.012 mol) of 4,4 '- (1-methylethylidene) bis [2,6-bis (methoxymethyl) -4-methoxybenzene] was added to THF (100 g) And then slowly inserted. Then, the temperature was slowly raised to room temperature. After standing for 3 hours, the reaction was terminated by monitoring with TLC. To the reaction mixture is poured 1000 ml of ethyl acetate, stirring is continued, and then only the organic layer is extracted using a separating funnel. 500 ml of water is again added to the separating funnel and the remaining impurities are removed by shaking. The organic layer is finally extracted after repeating the process three times or more.

The flask was charged with 9,9 ', 9 ", 9"' - (5,5 ', 5 ", 5'" - (5,5 '- (propane- tetrais (6-methoxynaphthalene-5,2-diyl) tetrakis (9- (6-methoxynaphthalen-2-yl) -9H- After adding 100 g (0.0450 mol) of fluorene, 91.1 g (0.450 mol) of 1-dodecan sulfate, 30.3 g (0.540 mol) of potassium hydroxide and 350 g of N, N- dimethylformamide, Lt; / RTI > The mixture was then cooled and neutralized to pH 7 with 5% hydrogen chloride solution. The precipitate formed was filtered to obtain 1,1 ', 1 ", 1"' - (5,5 '- (propane-2,2-diyl ) bis (2-hydroxybenzene-5,3,1-triyl) tetrakis (methylene) tetrakis (6- (9- (6-hydroxynaphthalen- 2- yl) -9H- fluoren-9-yl) naphthalen- ). The organic solution was then concentrated with an evaporator, and 700 g of tetrahydrofuran was added to the obtained compound to obtain a solution state. The solution was slowly added dropwise to a beaker containing 3000 ml of hexane being stirred to form a precipitate to obtain a polymer represented by the following formula (A). The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using Gel Permeation Chromatography (GPC). (Mw: 2,000, PD: 1.11)

(A)

In formula (A), n1, n2, n3 and n4 are each independently 0 or 1.

Synthetic example  2

20 g (0.044 moles) of bis-9,9-naphtholfluorene was dissolved in DMF together with potassium carbonate and methyl iodide, methylated with -OH and placed in tetrahydrofuran (180 g) in a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube The temperature was lowered to -78 deg. C and dissolved by stirring for 3 hours. 6.2 g (0.097 mol) of n-butyllithium was slowly added thereto, followed by stirring for 1 hour. 5 g (0.012 mol) of 4,4 '- (1-methylethylidene) bis [2,6-bis (methoxymethyl) -4-methoxybenzene] was added to THF (100 g) And then put it in quickly. Then, the temperature was slowly raised to room temperature. After standing for 3 hours, the reaction was terminated by monitoring with TLC. To the reaction mixture is poured 1000 ml of ethyl acetate, stirring is continued, and then only the organic layer is extracted using a separating funnel. 500 ml of water is again added to the separating funnel and the remaining impurities are removed by shaking. The organic layer is finally extracted after repeating the process three times or more.

The flask was charged with 9,9 ', 9 ", 9"' - (5,5 ', 5 ", 5'" - (5,5 '- (propane- tetrais (6-methoxynaphthalene-5,2-diyl) tetrakis (9- (6-methoxynaphthalen-2-yl) -9H- fluorene in an amount of 100 g (0.0450 mol), 91.1 g (0.450 mol) of 1-dodecan sulfate, 30.3 g (0.540 mol) of potassium hydroxide and 350 g of N, N- dimethylformamide, Lt; / RTI > The mixture was then cooled and neutralized to pH 7 with 5% hydrogen chloride solution. The precipitate formed was filtered to obtain 1,1 ', 1 ", 1"' - (5,5 '- (propane-2,2-diyl ) bis (2-hydroxybenzene-5,3,1-triyl) tetrakis (methylene) tetrakis (6- (9- (6-hydroxynaphthalen- 2- yl) -9H- fluoren-9-yl) naphthalen- ). The organic solution was then concentrated with an evaporator, and 700 g of tetrahydrofuran was added to the obtained compound to obtain a solution state. This solution was slowly added dropwise to a beaker containing 3000 ml of hexane being stirred to form a precipitate to obtain a polymer represented by the following formula (B). The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using Gel Permeation Chromatography (GPC). (Mw: 6,500, PD: 1.2)

[Chemical Formula B]

In the formula (B), n1, n2, n3 and n4 are each independently 0 or 1.

Synthetic example  3

20 g (0.044 moles) of bis-9,9-naphtholfluorene was dissolved in DMF together with potassium carbonate and methyl iodide, methylated with -OH and placed in tetrahydrofuran (180 g) in a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube The temperature was lowered to -78 deg. C and dissolved by stirring for 3 hours. 6.2 g (0.097 mol) of n-butyllithium was slowly added thereto, followed by stirring for 1 hour. 5 g (0.012 mol) of perylene, 3,4,9,10-tetrakis (methoxymethyl) was added to THF (100 g), and the temperature was lowered to -78 ° C., followed by stirring for 3 hours to dissolve. Then, the temperature was slowly raised to room temperature. After standing for 3 hours, the reaction was terminated by monitoring with TLC. To the reaction mixture is poured 1000 ml of ethyl acetate, stirring is continued, and then only the organic layer is extracted using a separating funnel. 500 ml of water is again added to the separating funnel and the remaining impurities are removed by shaking. The organic layer is finally extracted after repeating the process three times or more.

The flask was charged with 3,4,9,10-tetrakis (3-methoxy-7- (9- (6-methoxynaphthalen-2-yl) -9H- fluoren- (0.450 mol) of 1-dodecane oxide, 30.3 g (0.540 mol) of potassium hydroxide and 350 g of N, N-dimethylformamide were added to the mixture at 120 DEG C Stir for 8 hours. The mixture was then cooled and neutralized to pH 7 with 5% hydrochloric acid solution. The precipitate formed was filtered to obtain 3,3 ', 3 ", 3' '- (perylene-3,4,9,10-tetrayltetrakis ))) tetrakis (6- (9- (6-hydroxynaphthalen-2-yl) -9H-fluoren-9-yl) naphthalen-2-ol. The organic solution was then concentrated with an evaporator, and 700 g of tetrahydrofuran was added to the obtained compound to obtain a solution state. This solution was slowly added dropwise to a beaker containing 3000 ml of hexane being stirred to form a precipitate to obtain a polymer represented by the following formula (C). The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using Gel Permeation Chromatography (GPC). (Mw: 2,000, PD: 1.1)

≪ RTI ID = 0.0 &

In the formula (C), n1, n2, n3 and n4 are each independently 0 or 1.

Comparative Synthetic Example  One

In a flask, 82 g of 4,4 '- (9H-fluorene-9,9-diyl) diphenol (38 g), 1,4- bis (methoxymethyl) benzene (17 g), propylene glycol monomethyl ether acetate (PGMEA) 0.5 g of diethylsulfate was added thereto, followed by stirring at 100 ° C for 2 to 15 hours to carry out a polymerization reaction. The reaction was completed when the weight average molecular weight was 2,000 to 3,500. After completion of the polymerization reaction, the reaction product was gradually cooled to room temperature, and then the reaction product was added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). After stirring vigorously using 320 g of methanol and 320 g of water, the solution was allowed to stand (first step). The resulting supernatant was again removed and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a compound (Mw: 3,700) having a structural unit represented by the following formula (D).

[Chemical Formula D]

Hard mask  Preparation of composition

Example  One

1.2 g of the compound obtained in Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v) Of a Teflon filter to produce a hard mask composition.

Example  2

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 2 was used instead of the compound obtained in Synthesis Example 1.

Example  3

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 2 was used instead of the compound obtained in Synthesis Example 1.

Comparative Example  One

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 1 was used instead of the compound obtained in Synthesis Example 1.

Evaluation 1: Solubility experiment

When the hard mask composition according to Examples 1 to 2 and Comparative Example 1 was dissolved in propylene glycol monoethyl ether acetate (PGMEA) at a concentration of 10%, it was confirmed whether or not there was insoluble part.

The results are shown in Table 1 below.

In the solubility evaluation column of Table 2, "o" means that no solid content was observed when visually observed, and "X" means that solid content remained when observed with naked eyes.

Solubility assessment Example 1 ○ Example 2 ○ Comparative Example 1 ○

Evaluation 2: Step  Characteristic experiment

The patterned wafers were coated with the hard mask composition according to Examples 1 to 2 and Comparative Example 1, baked, and then gap-fill and planarization characteristics were observed using V-SEM equipment.

The step characteristic is numerically expressed by the following equation (1). 2 is a reference diagram for explaining calculation formula 1 for calculating a step sum. Referring to FIG. 2, the step characteristics are better as the difference in the thickness of the peri portion without cells and the coating thickness on the cells is small. Referring to FIG. 2, since the film thickness in the cell portion varies depending on the distance from the ferry, four cells are selected in the order close to the ferry, and the smaller the sum of the steps of the cell and the ferry region is, .

[Equation 1]

(Nm) = (h0-h1) + (h0-h2) + (h0-h3) + (h0-h4)

Evaluation 3: Gap-fill and planarization characteristics experiment

The hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-coated on a silicon wafer by adjusting the mass ratio of the solvent to the solute to 7 to 93 and then subjected to a baking process to observe the cut surfaces using V-SEM . Under the above conditions, the thickness of the mask on the bare wafer was about 1100 ANGSTROM.

The gap-fill and planarization characteristics were determined by observing the cross-section of the pattern using a scanning electron microscope (SEM) to determine whether or not a void was generated. The planarization characteristic was evaluated as a step difference (h ₁ -h ₂ ) Were measured. Referring to equation 2 of Figure 3, h1 is an arbitrary three points of mean value by averaging the film thickness measured at any three points in that a pattern is formed on the substrate and, h ₂ is formed in a pattern on the substrate Quot; means the thickness of the thin film measured in the " Referring to FIG. 3, the planarization characteristic is superior as the difference between h ₁ and h ₂ is small.

The results of the evaluations 2 and 3 are shown in Table 2 below.

Flatness of membrane Gap Fill Character
(Whether void is generated) Step total
(nm) Planarization characteristics
(%) Example 1 23 25 X Example 2 16 24 X Example 3 28 28 X Comparative Example 1 172.8 59 X

Referring to Table 2, the thin film formed from the hard mask composition according to Examples 1 and 2 has a step sum according to Equation 1 and a planarization property according to Equation 2 are relatively higher than those formed from the hard mask composition according to Comparative Example 1. [ And it has a good film flatness.

Rating 4: Awareness of corrosion  Experiment

The hard mask composition (polymer content: 9.5%) according to Examples 1 to 2 and Comparative Example 1 was coated on a silicon wafer by a spin-on coating method on a patterned silicon wafer. Then, a thin film was formed by heat treatment at 400 ° C for 120 seconds, and then the thickness of the thin film was measured using a ST-5000 thin film thickness gauge of K-MAC.

Then, after performing dry etching for 60 seconds each using N ₂ / O ₂ mixed gas _{(50mT / 300W / 10O 2 /} 50N 2) to the thin film was further measured the thickness of the thin film. The bulk etch rate (BER) was calculated from the thin film thickness before and after the dry etching and the etching time according to the following equation (1).

The dry etching was performed for 120 seconds using CFx gas (100mT / 600W / 42CF ₄ / 600Ar / 15O ₂ ) instead of the N ₂ / O ₂ mixed gas and the etching rate was similarly calculated by the following formula 3.

[Equation 3]

Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etching time (Å / sec)

Evaluation 5: Heat resistance test

The hard mask composition (10.0% by weight) according to Examples 1 to 2 and Comparative Example 1 was spin-coated on a silicon wafer and then heat-treated at 240 ° C for 1 minute to measure the thickness of the thin film thickness meter of K- Respectively. Thereafter, the substrate was heat-treated at 400 ° C for 2 minutes, and then its thickness was measured again. From the thickness of the film measured at the two temperatures, the degree of relative heat resistance of the hard mask film was numerically calculated by calculating the thickness reduction ratio based on the following equation (4).

[Equation 4]

Thin film thickness reduction ratio = (thin film thickness after baking at 240 占 폚 - thin film thickness after baking at 400 占 폚) / (thin film thickness after baking at 240 占 폚) X100 (%)

The results of the evaluations 4 and 5 are shown in Table 3 below.

Etch rate (Å / s) Heat resistance (%)
(TGA) CFx N ₂ / O ₂ Example 1 28 27 95 Example 2 29 27 97 Example 3 24 23 98 Comparative Example 1 29 30 90

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.

Claims (14)

A moiety represented by the following formula (1), and
A moiety containing a fluorene structure
Containing
Compounds having a dendrimer structure:
[Chemical Formula 1]

In Formula 1,
X is a substituted or unsubstituted C6 to C50 aromatic ring group,
Y is a group represented by the following formula 2:
(2)

In Formula 2,
R ¹ and R ² are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
n is an integer from 0 to 5,
* Is the connection point. The method of claim 1,
Wherein X in Formula (1) is any one of a substituted or unsubstituted ring group listed in the following Group 1:
[Group 1]

In the group 1,
R ^a is a direct bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof. The method of claim 1,
Wherein said compound is represented by any one of the following formulas (3) to (5):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,
A is a moiety represented by the above formula (1)
B is a moiety comprising a fluorene structure,
D is

Wherein A and B are as defined above and * is a connection point,
a to t are independently 0 or 1, at least one of a to d in the formulas (3) to (5) is 1, at least one of e to h in the formulas (4) and (5) is 1, At least one of t is 1. The method of claim 1,
Wherein the moiety containing the fluorene structure is any one of a substituted or unsubstituted ring group selected from the following Group 2:
[Group 2]

The method of claim 1,
A compound having a weight average molecular weight of 500 to 200,000. A compound having a dendrimer structure including a moiety represented by the following formula 1 and a moiety having a fluorene structure, and
menstruum
: ≪ / RTI >
[Chemical Formula 1]

In Formula 1,
X is a substituted or unsubstituted C6 to C50 aromatic ring group,
Y is a group represented by the following formula 2:
(2)

In Formula 2,
R ¹ and R ² are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
n is an integer from 0 to 5,
* Is the connection point. The method of claim 6,
Wherein X in Formula 1 is any one of a substituted or unsubstituted ring group listed in Group 1 below:
[Group 1]

In the group 1,
R ^a is a direct bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, a substituted or unsubstituted C6 to C30 aryl A substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof. The method of claim 6,
Wherein the compound is represented by any one of the following Chemical Formulas 3 to 5:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,
A is a moiety represented by the above formula (1)
B is a moiety comprising a fluorene structure,
D is

Wherein A and B are as defined above and * is a connection point,
a to t are independently 0 or 1, at least one of a to d in the formulas (3) to (5) is 1, at least one of e to h in the formulas (4) and (5) is 1, At least one of t is 1. The method of claim 6,
Wherein the moiety having the fluorene structure is any one of a substituted or unsubstituted ring group selected from the following Group 2:
[Group 2]

The method of claim 6,
Wherein the compound has a weight average molecular weight of 500 to 200,000. The method of claim 6,
Wherein the compound is contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the organic film composition. Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 6 to 11 on the material layer,
Heat treating the organic film composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern,
Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
≪ / RTI > The method of claim 12,
Wherein the step of applying the organic film composition is performed by a spin-on coating method. The method of claim 12,
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.

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