KR20120004192A - Aromatic ring-containing compound for resist underlayer, resist underlayer composition including same, and method of patterning device using same - Google Patents

Abstract

PURPOSE: An aromatic ring-containing compound for a resist under-layer, a resist under-layer composition including the same, and a pattern forming method for a device using the same are provided to improve the optical characteristic, the mechanical characteristic, and the etching selectivity of the compound. CONSTITUTION: An aromatic ring-containing compound includes repeating units represented by chemical formulas 1-1 and 1-2. In the chemical formula 1-1, the m is more than or equal to 1 and is less than 190. The p is 1 or 2. The Ar is an aromatic ring. The X is hydroxyl group, substituted or non-substituted C1-C10 alkoxy group, or substituted or non-substituted C6-C30 aryloxy group. The Ra is hydrogen, substituted or non-substituted C1-C10 alkyl group, substituted or non-substituted C3-C8 cycloalkyl group, substituted or non-substituted C6-C30 aryl group, substituted or non-substituted C2-C10 alkenyl group, or halogen. In the chemical formula 1-2, the n is more than or equal to 1 and is less than 190. The Ra and the Rc are identical or different and are hydrogen, substituted or non-substituted C3-C8 cycloalkyl group, or substituted or non-substituted C6-C30 aryl group.

Description

Aromatic ring-containing compound for resist underlayer film, resist underlayer film composition comprising the same, and pattern formation method of device using same.

The present disclosure relates to an aromatic ring-containing compound for resist underlayer films, a resist underlayer film composition comprising the compound, and a pattern forming method of a device using the same.

There is a continuing need to reduce the size of structural features in the microelectronics industry and in the industrial sector of microscopic structures (eg, micromachines, magnetoresist heads, etc.). In addition, there is a need in the microelectronics industry to reduce the size of microelectronic devices, thereby providing a larger amount of circuitry for a given chip size.

To reduce this shape size, effective lithographic techniques are essential.

A typical lithographic process first applies a resist to an underlying material and then exposes it to radiation to form a resist layer. The resist layer is then developed with a developer to form a patterned resist layer, and the material in the openings of the patterned resist layer is etched to transfer the pattern to the underlying material. After the transfer is completed, the remaining resist layer is removed.

However, in some cases, the resist may not have sufficient resistance to an etching step to effectively transfer a predetermined pattern to the underlying material. Therefore, when an ultra thin resist layer using an extremely thin resist material is required, when the substrate to be etched is thick, or when an etching depth is required deeply, it is necessary to use a specific etchant for a given underlayer material. In some cases, a resist underlayer film has been used.

The resist underlayer film serves as an intermediate layer between the resist layer and the substrate to be patterned, and serves to transfer the pattern of the patterned resist layer to the underlayer material, and thus must withstand the etching process required to transfer the pattern.

Many materials have been attempted to form such underlayer films, but there is still a need for improved underlayer compositions.

Conventional materials for forming resist underlayer films are difficult to apply to substrates, for example using chemical or physical vapor deposition, special solvents, and / or high temperature firing, but these are expensive problems. Therefore, in recent years, research on the resist underlayer film composition which can be applied by a spin-coating technique without performing high temperature baking is progressing. In addition, it is possible to easily etch selectively using a resist layer formed on top as a mask, and at the same time, when the lower layer is a metal layer, at the same time, the lower layer film resistant to the etching process required for patterning the lower layer using the lower layer layer as a mask. Studies on the composition are in progress.

In addition, studies on underlayer film compositions that provide adequate shelf life and avoid interfering interactions with the resist layer (e.g., contaminating the resist or substrate by an acid catalyst included in the underlayer film composition) In addition, research is underway on the underlayer film composition having predetermined optical properties for radiation of shorter wavelengths (eg, 157 nm, 193 nm or 248 nm).

In conclusion, it is desirable to perform lithographic techniques using antireflective compositions that have high etch selectivity, sufficient resistance to multiple etching, and minimize reflectivity between the resist and underlying material. This lithographic technology will enable the production of very detailed semiconductor devices.

One aspect of the present invention is to provide an aromatic ring-containing compound for resist underlayer films having excellent optical properties, mechanical properties, and etch selectivity properties, which can be applied using a spin-on application technique. will be.

Another aspect of the present invention is to provide a resist underlayer film composition including the compound is excellent in the etching selectivity to provide sufficient resistance to multiple etching, and does not use the acid catalyst, there is no contamination problem due to the use of the acid catalyst It is.

Another aspect of the present invention is to provide a method of forming a device pattern using the resist underlayer film composition.

One aspect of the present invention is to provide an aromatic ring-containing compound comprising a repeating unit represented by the following formula 1-1 and a repeating unit represented by the following formula 1-2.

[Formula 1-1]

In Chemical Formula 1-1,

m is in the range 1 ≦ m <190.

p is an integer of 1 or 2,

Ar is an aromatic ring group,

X is a hydroxy group (-OH), a substituted or unsubstituted C1 to C10 alkoxy group or a substituted or unsubstituted C6 to C30 aryl oxy group,

R _a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a halogen group to be.

[Formula 1-2]

In Chemical Formula 1-2,

n is in the range of 1 ≦ n <190, R _a and R _c are the same as or different from each other, and are hydrogen, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, provided that R _a and R _c are not simultaneously hydrogen.

In Formula 1-2, n may be 1 ≦ n <40 or n may be in a range of 1 ≦ n <20.

The weight average molecular weight of the aromatic ring-containing compound may be 2,000 to 10,000.

Another aspect of the present invention provides a resist underlayer film composition comprising an aromatic ring-containing compound and an organic solvent comprising a repeating unit represented by Chemical Formula 1-1 and a repeating unit represented by Chemical Formula 1-2.

The resist underlayer film composition may further include a surfactant or a crosslinking component.

Another aspect of the present invention provides a method of manufacturing a semiconductor device, the method comprising: (a) providing a layer of material on a substrate; (b) forming an underlayer film on the material layer using the resist underlayer film composition; (c) forming a resist layer on the underlayer film; (d) exposing the substrate on which the resist layer is formed; (e) developing the exposed substrate; And (f) etching the developed substrate.

In the manufacturing method, a step of forming a silicon-containing resist underlayer film may be further performed before the step (c) of forming a resist layer.

In addition, a step of forming a bottom anti-reflective coating (BARC) may be further performed before the forming of the (c) resist layer.

The aromatic ring containing compound has very good optical properties, mechanical properties and etching selectivity properties. In addition, the underlayer film composition including the compound may be applied to a substrate by a spin-on coating technique, is useful for a shorter wavelength lithographic process, and there is no problem of contamination by an acid catalyst.

In addition, the composition containing the compound may minimize the reflectivity between the resist and the material layer by having a refractive index and absorbance of the range useful as an antireflection film in the DUV (Deep UV) region, such as the ArF (193nm) wavelength region when forming the film. In this way, it is possible to provide a lithographic structure having an excellent pattern forming ability in the pattern profile or margin. In addition, when performing lithographic techniques, the etching selectivity is very high compared to the existing materials, and the resistance to multiple etching is sufficient, so that the etch profile of the underlayer film, which is an image to be transferred to the lower layer, is very good.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, "substituted" means substituted with a hydroxy group, a halogen, a C1 to C10 alkyl group, a C5 to C20 aryl group or a C2 to C10 alkenyl group. The aromatic ring group means a functional group in the form of electron delocalization or resonance, and means an aryl group, heteroaryl group, and the like. The heteroaryl group means containing 1 to 3 heteroatoms of N, O, S or P in the ring.

Unless otherwise specified, the alkyl group is a C1 to C10 alkyl group, the aryl group is a C6 to C20 aryl group, and the alkenyl group is a C2 to C10 alkenyl group such as a vinyl group or an allyl group.

According to one embodiment of the present invention, an aromatic ring-containing compound for a resist underlayer film including a repeating unit represented by the following Formula 1-1 and a repeating unit represented by the following Formula 1-2 is provided.

[Formula 1-1]

In Chemical Formula 1-1,

m is in the range 1 ≦ m <190.

p is an integer of 1 or 2,

Ar is an aromatic ring group,

X is a hydroxy group (-OH), a substituted or unsubstituted C1 to C10 alkoxy group or a substituted or unsubstituted C6 to C30 aryl oxy group,

Ra is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a halogen group .

[Formula 1-2]

In Chemical Formula 1-2,

n is in the range of 1 ≦ n <190,

R _a and R _c are the same as or different from each other, and are hydrogen, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, provided that R _a and R _c are not simultaneously hydrogen.

An aromatic ring-containing compound comprising a repeating unit represented by Chemical Formula 1-1 and a repeating unit represented by Chemical Formula 1-2 has an aromatic ring having strong absorption in a short wavelength region (particularly, 193 nm and 248 nm). Since it is included in the skeleton portion of the compound, it can be used as an antireflection film. In addition, by having the functional groups represented by X and R _a in the side chain, the etching selectivity is excellent, and the resistance to multiple etching, the heat resistance, and the like are excellent.

In Formula 1-2, n may be 1 ≦ n <40 or n may be in a range of 1 ≦ n <20. By adjusting the molar ratio of the repeating unit represented by Formula 1-1 and the repeating unit represented by Formula 1-2 to a preferred range, etching selectivity, resistance to multiple etching, heat resistance, and the like may be further improved.

The aromatic ring group (Ar) in Chemical Formula 1-1 may be selected from the group consisting of the following Chemical Formulas 2 to 13.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Formula 13]

In Chemical Formulas 2 to 13,

R ₁ to R ₄₄ are each independently hydrogen, a hydroxy group, an alkyl group, an aryl group, an alkenyl group or a halogen group,

h ₁ to h ₄₄ are each independently 0 to k-2, where k corresponds to the total number of H that may be present in each aromatic ring.

In Formula 1-1, R _a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C10 alkenyl group or halogen group.

R _a may be an aryl group represented by Formulas 14 to 25.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

(23)

[Formula 24]

[Formula 25]

In Chemical Formulas 14 to 25,

Y ₁ to Y ₄₄ are each independently hydrogen, a hydroxy group, an alkyl group, an aryl group, an alkenyl group or a halogen group,

r1 to r44 are each independently 0 to k-1, where k corresponds to the total number of H that may be present in each aromatic ring.

R _a in Formula 1-1 and R _c in Formula 1-2 are the same as or different from each other, and are hydrogen, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, provided R _a and R _c are not simultaneously hydrogen.

R _a in Formula 1-1 and R _c in Formula 1-2 may be aryl groups represented by Formulas 26 to 37.

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

In Chemical Formulas 26 to 37,

Z ₁ to Z ₄₄ are each independently hydrogen, a hydroxy group, an alkyl group, an aryl group, an alkenyl group or a halogen group,

s1 to s44 are each independently 0 to k-1, where k corresponds to the total number of H that may be present in each aromatic ring.

The weight average molecular weight of the aromatic ring-containing compound may be about 2,000 to 10,000. When the weight average molecular weight of the aromatic ring-containing compound is included in the above range, the desired coating thickness can be realized or a good thin film can be formed .

Another embodiment of the present invention provides an underlayer film composition comprising an aromatic ring-containing compound. The aromatic ring-containing compound is a compound including a repeating unit represented by Formula 1-1 and a repeating unit represented by Formula 1-2.

In addition, the resist underlayer film composition includes an organic solvent. It will not specifically limit, if it is an organic solvent which has sufficient solubility with respect to the said polymer as this organic solvent. However, representative examples of organic solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate. lactate), gamma-butyrolactone (GBL), acetyl acetone, and the like.

In the lower layer film composition according to the embodiment of the present invention, the content of the aromatic ring-containing compound may be 1 to 20% by weight, more preferably 3 to 10% by weight. When the content of the aromatic ring-containing compound is included in the above range, the composition can be appropriately adjusted to the desired coating thickness when forming the underlayer film.

In addition, the content of the organic solvent may be the remainder, that is, 80 to 99% by weight, when the content of the organic solvent is included in the above range, by applying the composition to adjust the desired coating thickness to the desired coating thickness when forming the underlayer film Can be.

The underlayer film composition according to the embodiment of the present invention may further include an acid catalyst. In this case, the content of the acid catalyst may be 0.001 to 0.05 parts by weight based on 100 parts by weight of the underlayer film composition. When the content of the acid catalyst is included in the above range, it is possible to obtain desirable crosslinking properties, it is possible to excellently improve the storage stability. Examples of the acid catalyst include p-toluenesulfonic acid mono hydrate, pyridinium p-toluene sulfonate, and 2,4,4,6-tetrabromocyclohexadienone. , Benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acid, but may be selected from the group.

The underlayer film composition according to one embodiment of the present invention may further include a surfactant. In this case, the content of the surfactant may be 0.01 to 1 part by weight based on 100 parts by weight of the underlayer film composition. When the content of the surfactant is included in the above range, it is advantageous to implement the coating performance of the underlayer film composition to be formed. The surfactant may be an alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycols, quaternary ammonium salts, etc., but is not limited thereto.

The underlayer film composition according to one embodiment of the present invention may further include a crosslinking component. The content of the crosslinking component may be 0.1 to 5 parts by weight based on 100 parts by weight of the underlayer film composition, and more preferably 0.1 to 3 parts by weight. When the content of the crosslinking component is included in the above range, appropriate crosslinking properties can be obtained without changing the optical properties of the underlayer film to be formed.

Specific examples of the crosslinking component include etherified amino resins such as methylated or butylated melamine resins (specific examples being N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin) and methylation. Or butylated urea resins (specific examples are Cymel U-65 Resin or UFR 80 Resin), glycoluril derivatives represented by the following formula 38 (specific examples are Powderlink 1174), 2,6-bis (hydr Oxymethyl) -p-cresol compound). In addition, a bisepoxy-based compound represented by the following Chemical Formula 39 and a melamine derivative represented by the following Chemical Formula 40 may also be used as the crosslinking component.

[Formula 38]

[Formula 39]

[Formula 40]

Another embodiment of the present invention provides a method of forming a pattern of a device using a resist underlayer film composition, comprising: (a) providing a material layer on a substrate; (b) forming an underlayer film on the material layer using the resist underlayer film composition; (c) forming a resist layer on the underlayer film layer; (d) exposing the substrate on which the resist layer is formed; (e) developing the exposed substrate; And (f) etching the developed substrate.

Hereinafter, this pattern formation method is demonstrated in detail.

First, a material layer is formed on a substrate.

As the substrate, a silicon substrate may be used, and the material constituting the material layer may be any conductive, semiconducting, magnetic or insulating material, and representative examples thereof include aluminum and silicon nitride (SiN). have. Since the method of forming the material layer is a conventional method, detailed description thereof will be omitted.

Subsequently, an underlayer film is formed using a resist underlayer film composition according to an embodiment of the present invention. The underlayer film forming process may be formed by coating the resist underlayer film composition to a thickness of 500 to 4000 kPa and baking. The coating process may be performed by a spin coating process, and the baking process may be performed at 100 to 500 ° C. for 10 seconds to 10 minutes. The coating process, the thickness of the underlayer film, the baking temperature and time is not limited to the above range, can be prepared in a variety of different forms, those skilled in the art to which the present invention belongs It will be understood that other specific forms may be practiced without changing the essential features.

When an underlayer film is formed, a resist layer (photosensitive imaging layer) is formed on this underlayer film layer. Since the resist layer may be performed by a generally known process of coating and baking the photosensitive resist composition, detailed description thereof will be omitted herein.

Before forming the resist layer, a step of forming a silicon-containing resist underlayer film may be further performed, or a step of forming an antireflection layer may be further performed. Of course, after forming a silicon-containing resist underlayer film, you may perform all the processes of forming an antireflection layer. Since the silicon-containing resist underlayer film and the anti-reflection layer are well known in the art, detailed description thereof will be omitted herein.

Subsequently, the resist layer is exposed. This exposure process is performed using various exposure sources, for example, ArF or EUV (extreme UV), an E-beam, and the like. When the exposure is completed, a baking process is performed to cause a chemical reaction in the exposure area. This baking process may be carried out for about 60 to 90 seconds in the temperature range of about 90 to 120 ℃.

Then, a development process is performed to remove the lower layer film and the resist layer. The said developing process can be performed with basic aqueous solution. As the basic aqueous solution developer, an aqueous tetramethylammonium hydroxide (TMAH) solution may be used. When the exposure source used is an ArF excimer laser, a line and space pattern of 80 to 100 nm may be formed at a dose of about 5 to 30 mJ / cm 2.

The resist pattern obtained from the process as described above is used as a mask, and is etched using a specific etching gas, for example, a halogen gas or a plasma such as a fluorocarbon gas such as CHF ₃ , CF _4, or the like. The stripper may then be used to remove the resist pattern remaining on the substrate to form the desired pattern.

According to this process, a semiconductor integrated circuit device can be provided.

Thus, the compositions of the present invention and formed lithographic structures can be used in the manufacture and design of integrated circuit devices in accordance with conventional semiconductor device fabrication processes. For example, it can be used to form patterned material layer structures, such as metal wiring, holes for contact or bias, insulation sections (e.g., damascene or shallow trench isolation), trenches for capacitor structures, and the like. Can be. It is also to be understood that the invention is not limited to any particular lithographic technique or device structure.

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

Synthetic example  1: 1- With pyreneethanol Benzoaldehyde  Synthesis of Copolymer

A nitrogen gas was introduced into a 500 m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube. , PGMEA) and stir well. After 15 minutes, 2.86 g (0.015 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 100 to 12 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. The solution was placed in a separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing monomer, thereby obtaining a polymer represented by the following formula (Mw = 4,400, polydispersity = 1.19, n = 10.8).

[Formula 41]

Synthetic example  2: containing naphthalene Pyren and Benzoaldehyde  Copolymer synthesis

Nitrogen gas was introduced into a 500 m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 69.1 g (0.30 mol) of pyrene carboaldehyde and 38.2 g of benzoaldehyde were contained in 257 g of propylene glycol monomethyl ether acetate. Stir well. After 15 minutes, 2.86 g (0.015 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 100 to 12 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. This solution was put into a separatory funnel, n-heptane was added to this, the low molecular weight containing a monomer was removed, and the polymer was obtained. Nitrogen gas was introduced into a 500 m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 20 g of the polymer was added to 261 g of tetrahydrofuran (THF) and stirred well. After 10 minutes, 62.8 ml of 1 mol of naphthyl magnesium bromine solution dissolved in THF was slowly added thereto, followed by reaction for 6 hours. After completion of the reaction, the resultant was concentrated by an evaporator, magnesium salt was removed using water and dichloromethane, and then concentrated by an evaporator, and then adjusted to a solution of 20 wt% concentration. The solution was placed in a separatory funnel, and n-heptane was added thereto to precipitate to obtain a polymer represented by the following chemical formula (Mw = 3,100, polydispersity = 1.39, n = 9.7).

[Formula 42]

Synthetic example  3: Phenyl  Containing With hydroxypyrene  2-naphthalene Carboaldehyde  Synthesis of Copolymer

Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, and 547.5 g (0.22 mol) of hydroxypyrene carboaldehyde and 41.2 g of 2-naphthalaldehyde were 227.5 g of propylene glycol. It was contained in monomethyl ether acetate and stirred well. After 15 minutes, 2.10 g (0.011 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 100 to 24 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. This solution was put into a separatory funnel, n-heptane was added to this, the low molecular weight containing a monomer was removed, and the polymer was obtained. Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 20 g of the polymer was placed in 223 g of tetrahydrofuran and stirred well. After 10 minutes, 53.8 ml of 1 mol of phenylmagnesium bromine solution dissolved in THF was slowly added thereto, followed by reaction for 6 hours. After completion of the reaction, the resultant was concentrated by an evaporator, magnesium salt was removed using water and dichloromethane, and then concentrated by an evaporator, and then adjusted to a solution of 20 wt% concentration. The solution was placed in a separatory funnel, and n-heptane was added thereto to precipitate to obtain a polymer represented by the following Chemical Formula 43 (Mw = 2,800, polydispersity = 1.31, n = 5.1).

[Formula 43]

Synthetic example  4: Phenyl  Containing Perylene and Hexanal  Synthesis of Copolymer

Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 70.1 g (0.22 mol) of perylene carboaldehyde and 30.4 g of hexanal were added to 230 g of propylene glycol monomethyl ether acetate. Contain and stir well. After 15 minutes, 2.38 g (0.013 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 100 to 24 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. This solution was put into a separatory funnel, n-heptane was added to this, the low molecular weight containing a monomer was removed, and the polymer was obtained. Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 20 g of the polymer was placed in 223.4 g of tetrahydrofuran and stirred well. After 10 minutes, 39.8 ml of 1 mol of phenylmagnesium bromine solution dissolved in THF was slowly added thereto, followed by reaction for 6 hours. After completion of the reaction, the resultant was concentrated by an evaporator, and then magnesium salts were removed using water and dichloromethane. The solution was placed in a separatory funnel, and n-heptane was added thereto to precipitate to obtain a polymer represented by the following formula (44) (Mw = 2,200, polydispersity = 1.41, n = 4.2).

[Formula 44]

Synthetic example  5: containing naphthalene With chlorene   2-naphthalene Carboaldehyde  Synthesis of Copolymer

Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, and 56.2 g (0.22 mol) of chlorocarboaldehyde and 31.9 g of 2-naphthalene carboaldehyde were 209 g of propylene glycol mono Put in methyl ether acetate and stir well. After 15 minutes, 1.62 g (0.0085 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 130 at 24 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. This solution was put into a separatory funnel, n-heptane was added to this, the low molecular weight containing a monomer was removed, and the polymer was obtained. Nitrogen gas was introduced into a 500m four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, and 20 g of the polymer was placed in 235 g of tetrahydrofuran (THF) and stirred well. After 10 minutes, 41.8 ml of 1 mol of naphthyl magnesium bromine solution dissolved in THF was slowly added thereto, followed by reaction for 6 hours. After completion of the reaction, the resultant was concentrated by an evaporator, magnesium salt was removed using water and dichloromethane, and then concentrated by an evaporator, and then adjusted to a solution of 20 wt% concentration. The solution was placed in a separatory funnel, and n-heptane was added thereto to precipitate to obtain a polymer represented by the following Chemical Formula 45 (Mw = 2,100, polydispersity = 1.44, n = 3.0).

[Formula 45]

Comparative Synthesis Example  One: Fluorenylidenediphenol  1,4- Bismethoxymethylbenzene  Synthesis of Copolymer

8.75 g (0.05 mol) of a, a'-dichloro-p-xylene and aluminum chloride with nitrogen gas flowing into a 1-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube. ) Stir well with 26.66 g and 200 g of γ-butyrolactone. After 10 minutes, a solution of 35.03 g (0.10 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. . After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with methylamyl ketone (MAK) and methanol and adjusted to a solution of 15 wt% MAK / methanol = 4/1 (weight ratio). This solution was put into a three-liquid funnel, n-heptane was added to this to remove the low molecular weight containing a monomer, and the polymer represented by following formula (46) (Mw = 12,000, polydispersity = 2.0, n = 23) was obtained.

[Formula 46]

Comparative Synthesis Example  2: 1- With hydroxypyrene Paraformaldehyde  Copolymer synthesis

Nitrogen gas was introduced into a 500-meter four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, while 109.2 g (0.50 mol) of 1-hydroxypyrene and 18.2 g of paraformaldehyde were 308 g of propylene glycol monomethyl ether acetate. (Propyleneglycolmonomethyletheracetate, PGMEA) and stir well. After 15 minutes, 4.76 g (0.025 mol) of pyridinium p-toluene sulfonate was slowly added thereto, followed by reaction at 100 to 12 hours. After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. Then diluted with methanol and adjusted to a solution of 15 wt% concentration. The solution was placed in a separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing monomer, thereby obtaining a polymer represented by the following formula (Mw = 2,100, polydispersity = 1.22, n = 8.0).

[Formula 47]

Example  1 to 5

1.0 g of the polymers prepared in Synthesis Examples 1 to 5 were respectively weighed, and 0.1 g of a crosslinking agent (Powderlink 1174) represented by the following Chemical Formula 38 and 100 mg of pyridinium p-toluene sulfonate were dissolved in 9 g of cyclohexanone, and then filtered. To prepare a sample solution of Examples 1 to 5, respectively.

[Formula 38]

Each of the sample solutions prepared in Examples 1 to 5 was coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.

Comparative example  One

1.0 g of the polymer prepared in Comparative Synthesis Example 1, 0.1 g of crosslinking agent (Cymel 303), and 100 mg of pyridinium p-toluene sulfonate were dissolved in PGMEA 9 g, and then filtered to prepare a sample solution.

The prepared sample solution was coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.

Comparative example  2

1.0 g of the polymer prepared in Comparative Synthesis Example 2 was weighed, and 0.1 g of a crosslinking agent (Powderlink 1174) represented by the following Chemical Formula 38 and 100 mg of pyridinium p-toluene sulfonate were dissolved in 9 g of cyclohexanone, and then filtered. A solution was made.

The prepared sample solution was coated on a silicon wafer by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.

Refractive index and Extinction coefficient  Measure

The refractive index n and extinction coefficient k of the formed film were obtained, respectively. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1.

As shown in Table 1 it can be seen that the film prepared with the sample solution according to Examples 1 to 5 has a refractive index and absorbance (absorption coefficient) that can be used as an antireflection film at an ArF (193 nm) wavelength. On the other hand, the films prepared with the sample solutions of Comparative Examples 1 and 2 were found to have a refractive index and an absorbance that can be used as antireflection films at an ArF (193 nm) wavelength, but compared to Examples 1 to 5, the relatively low refractive index was confirmed. Could.

Pattern properties

The sample solutions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were respectively coated on a silicon wafer coated with aluminum by spin-coating, and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å.

The ArF photoresist was coated on each of the formed films, baked at 110 ° C. for 60 seconds, exposed to light using an ASML (XT: 1450G, NA 0.93) exposure apparatus, and developed using TMAH (2.38 wt% aqueous solution). And the line and space pattern of 60nm was examined using FE-SEM, respectively. The margin of focus (EL) margin according to the change of the exposure dose and the depth of focus (DoF) margin due to the distance change with the light source were examined. The results are shown in Table 2.

     The sample solutions prepared in Comparative Examples 1 and 2 were coated on a silicon wafer coated with aluminum by spin-coating and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å. The ArF photoresist was coated on the formed film, baked at 110 ° C. for 60 seconds, exposed to light using an exposure equipment of ASML (XT: 1450G, NA 0.93), and developed using TMAH (2.38 wt% aqueous solution). And the line and space pattern of 60nm was examined using FE-SEM. The margin of focus (DoF) margin due to the variation of the exposure latitude (EL) margin and the distance between the light source was investigated. The results are shown in Table 2.

As shown in Table 2, the films obtained with the sample solutions of Examples 1 to 5 showed good results in terms of pattern profile and margin. On the other hand, the films prepared with the sample solutions according to Comparative Examples 1 and 2 were found to be relatively disadvantageous in the pattern profile or margin, which may be due to the difference in absorption characteristics at ArF (193 nm) wavelength.

Etch  Selectivity evaluation

The sample solutions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were respectively coated on a silicon wafer coated with aluminum by spin-coating to bake at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å. The ArF photoresist was coated on each of the formed films, baked at 110 ° C. for 60 seconds, exposed to light using an ASML (XT: 1450G, NA 0.93) exposure apparatus, and then developed using TMAH (2.38 wt% aqueous solution), respectively. A line and space pattern was obtained.

  The sample solutions prepared in Comparative Examples 1 and 2 were coated on a silicon wafer coated with aluminum by spin-coating and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1500 Å. The ArF photoresist was coated on the formed film, baked at 110 ° C. for 60 seconds, exposed using ASML (XT: 1450G, NA 0.93) exposure equipment, and developed under TMAH (2.38 wt% aqueous solution) to give 60 nm line and space. (line and space) patterns were obtained.

The obtained patterned specimens were subjected to dry etching using CHF ₃ / CF ₄ mixed gas, respectively, followed by dry etching using BCl ₃ / Cl ₂ mixed gas, respectively. Finally, the remaining organics were removed using O ₂ gas, and then the sections were examined by FE-SEM. The results are shown in Table 3.

Samples Used to Make Film Pattern shape after etching Comparative Example 1 Tapered shape, rough surface Comparative Example 2 Tapered shape, rough surface Example 1 Vertical shape Example 2 Vertical shape Example 3 Vertical shape Example 4 Vertical shape Example 5 Vertical shape

From the results of Table 3, it was confirmed that the patterned specimens prepared with the sample solutions of Examples 1 to 5 had a good etch profile, which shows an excellent selectivity ratio. On the other hand, the patterned specimens prepared with the sample solutions of Comparative Examples 1 and 2 were able to confirm the taper phenomenon in the etch profile as a result of the etch evaluation, which is considered to be due to the lack of selectivity under the etch conditions.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims (16)

An aromatic ring-containing compound for a resist underlayer film comprising a repeating unit represented by Formula 1-1 and a repeating unit represented by Formula 1-2 below:

[Formula 1-1]

In Chemical Formula 1-1,
m is in the range 1 ≦ m <190.
p is an integer of 1 or 2,
Ar is an aromatic ring group,
X is a hydroxy group (-OH), a substituted or unsubstituted C1 to C10 alkoxy group or a substituted or unsubstituted C6 to C30 aryl oxy group,
R _a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a halogen group ,
[Formula 1-2]

In Chemical Formula 1-2,
n is in the range of 1 ≦ n <190,
R _a and R _c are the same as or different from each other, and are hydrogen, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, provided that R _a and R _c are not simultaneously hydrogen.
The method of claim 1,
N in the above formula 1-2 is an aromatic ring containing compound for resist underlayer film in the range of 1 ≤ n <40.
The method of claim 1,
In Formula 1-2, n is an aromatic ring-containing compound for resist underlayer films in the range of 1 ≦ n <20.
The method of claim 1,
Ar is an aromatic ring-containing compound for a resist underlayer film which is a functional group represented by one of the following Chemical Formulas 2 to 13
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Chemical Formula 8]

[Formula 9]

[Formula 10]

(11)

[Formula 12]

[Formula 13]

In Chemical Formulas 2 to 13,
R ₁ to R ₄₄ are each independently hydrogen, a hydroxy group, an alkyl group, an aryl group, an alkenyl group or a halogen group,
h1 to h44 are each independently 0 to k-2, where k corresponds to the total number of H that may be present in each aromatic ring.
The method of claim 1,
The said aromatic ring containing compound is an aromatic ring containing compound for resist underlayer films whose weight average molecular weights are 2,000-10,000.
A resist underlayer film composition comprising an aromatic ring-containing compound and an organic solvent comprising a repeating unit represented by the following Formula 1-1 and a repeating unit represented by the following Formula 1-2:
[Formula 1-1]

In Chemical Formula 1-1,
m is in the range 1 ≦ m <190.
p is an integer of 1 or 2,
Ar is an aromatic ring group,
X is a hydroxy group (-OH), a substituted or unsubstituted C1 to C10 alkoxy group or a substituted or unsubstituted C6 to C30 aryl oxy group,
R _a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C10 alkenyl group, or a halogen group ,
[Formula 1-2]

In Chemical Formula 1-2,
n is in the range of 1 ≦ n <190,
R _a and R _c are the same as or different from each other, and are hydrogen, a substituted or unsubstituted C3 to C8 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group, provided that R _a and R _c are not simultaneously hydrogen.
The method of claim 6,
N in the formula 1-2 is a resist underlayer film composition in the range of 1 ≤ n <40.
The method of claim 6,
N in the formula 1-2 is a resist underlayer film composition in the range of 1 ≤ n <20.
The method of claim 6,
Ar is a resist underlayer film composition which is a functional group represented by the formula of any one of Formulas 2 to 13:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Chemical Formula 8]

[Formula 9]

[Formula 10]

(11)

[Formula 12]

[Formula 13]

In Chemical Formulas 2 to 13,
R ₁ to R ₄₄ are each independently hydrogen, a hydroxy group, an alkyl group, an aryl group, an alkenyl group or a halogen group,
h1 to h44 are each independently 0 to k-2, where k corresponds to the total number of H that may be present in each aromatic ring.
The method of claim 6,
The content of the mixture of the aromatic ring-containing compound is 1 to 20% by weight of the resist underlayer film composition.
The method of claim 6,
The resist underlayer film composition is a resist underlayer film composition further comprising a surfactant.
The method of claim 6,
The resist underlayer film composition is a resist underlayer film composition further comprising a crosslinking component.
(a) forming a material layer on the substrate;
(b) forming an underlayer film on the material layer using the resist underlayer film composition according to any one of claims 6 to 12;
(c) forming a resist layer on the underlayer film layer;
(d) exposing the substrate on which the resist layer is formed;
(e) developing the exposed substrate; And
(f) etching the developed substrate
Pattern forming method of the device comprising a.
The method of claim 13,
And (c) forming a silicon-containing resist underlayer film on the resist underlayer film prior to forming the resist layer.
The method of claim 13,
And (c) forming an anti-reflective layer prior to forming the resist layer.
The method of claim 13,
And the device is a semiconductor integrated circuit device.