KR20190015060A - Composition for forming organic film - Google Patents

Abstract

The present invention provides a composition for forming organic film which can easily remove a silicon residue modified by dry etching in a wet manner by using a removing liquid harmless to a semiconductor apparatus substrate and an organic resist underlayer film required in the patterning process, for example, an ammonia aqueous solution containing hydrogen peroxide called SC1, which is commonly used in the semiconductor manufacturing process. There can be provided a composition for forming organic film, including a polymer compound having any one or more of repeating units represented by formulas (1) to (4), and an organic solvent. In the organic solvent, the total amount of at least one or more chemicals among propylene glycol ester, ketone, and lactone is more than 30 wt% of the total organic solvent.

Description

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

The present invention relates to a multilayer resist film material used for forming a wiring pattern on a substrate for semiconductor device production, and more particularly to a composition for forming an organic film.

Conventionally, high performance of the processing capability of the semiconductor device has led to miniaturization of the pattern size by shortening the wavelength of the light source in the lithography technique. However, since the speed of shortening the wavelength after the ArF light source has been slowed recently, it has been required to improve the processing capability of the semiconductor device instead of miniaturization. As one of such methods, there has been proposed a semiconductor device with high processing capability, in which three-dimensional transistors capable of operating at a higher speed than planar transistors are arranged at high density. A substrate for manufacturing such a semiconductor device (hereinafter referred to as a substrate) has a three-dimensional structure that is subjected to a complicated stepped process as compared with a conventional substrate. Therefore, if a pattern is formed by a pattern formation method using a single-layer photoresist used in forming a conventional planar transistor, the photoresist film follows the step formed during the processing of the substrate, As a result, a flat resist film can not be obtained. As a result, when the photoresist is exposed and patterned, the focus of the photoresist can not be precisely adjusted, resulting in a reduction in the yield of the substrate processing. New materials and methods are needed to prevent this.

As a method for solving such a problem, there is a multilayer resist method. In this method, a substrate having a step with a lower layer film having a high planarization performance is planarized, and a photoresist film is formed on the planarized film, thereby increasing the focus margin at the time of exposure, thereby preventing a reduction in the yield in processing the substrate. Further, in this method, when a lower layer film having different etching selectivity is selected for the upper layer photoresist film and the substrate, a pattern is formed on the upper layer resist film, and then the upper layer film pattern is dry- And the pattern can be transferred to the substrate to be processed by dry etching using the lower layer film as a dry etching mask.

As this multilayer resist method, a three-layer resist method which can be performed using a general resist composition used in a single layer resist method is generally used. For example, an organic resist underlayer film having a high degree of flatness and sufficient dry etching resistance for substrate processing is formed on a substrate to be processed, a silicon-containing resist underlayer film is formed thereon as an interlayer film (hereinafter referred to as a silicon-containing resist interlayer film) A photoresist film is formed as a resist overcoat film. With respect to the dry etching by the fluorine-based gas plasma, since the organic resist upper layer film has a good etching selectivity ratio with respect to the silicon-containing resist interlayer, the resist pattern can be transferred to the silicon-containing resist interlayer by using dry etching using a fluorine gas plasma have. In the case of dry etching by an oxygen-based gas plasma, since the silicon-based resist interlayer film has a good etching selectivity ratio with respect to the organic resist underlayer film, the silicon-containing resist interlayer pattern can be formed by dry etching using an oxygen- Can be transferred to the film. According to this method, a composition for forming a resist upper layer film which is difficult to form a pattern having a sufficient film thickness for directly processing a processed substrate and a composition for forming a resist upper layer film which is insufficient in dry etching resistance It is possible to obtain a pattern of the organic resist underlayer film having sufficient dry etching resistance to be processed, if the pattern can be transferred only to the silicon-containing film. Such pattern transfer by dry etching does not cause a problem such as pattern collapse due to friction caused by a developing solution at the time of developing a resist. Therefore, even if the aspect ratio is high, an organic film pattern having a thickness sufficiently functioning as a dry etching mask . By using the pattern of the organic resist underlayer film thus formed as a dry etching mask, it becomes possible to transfer a pattern to a substrate having a three-dimensional transistor structure having a complicated step. As described above, a lot of organic under-layer films are already known, such as those described in Patent Document 1, for example.

Generally, in the three-layer resist method, in order to stabilize the processing dimension, in pattern transfer by dry etching to the organic resist underlayer film, it is necessary to leave a silicon-containing resist interlayer of several nm thickness on the organic resist underlayer film pattern. The remaining silicon is etched away by the dry etching gas used to process the substrate while the pattern is being transferred to the substrate while the organic resist underlayer film pattern is used as a mask. Therefore, after the substrate is processed, Do not leave. Therefore, even if the organic resist underlayer film pattern remaining after the substrate processing is dry-etched (ashing) or wet-removed, the silicon content does not remain as residue on the substrate.

As described above, the multilayer resist method can be applied to a substrate on which a large step is formed as a substrate processing method, and thus is used for processing a wide range of substrates. Therefore, by using this feature, utilization as an ion implantation shielding mask in an ion implantation process, which is a part of a process for forming a three-dimensional transistor, is expected. However, in the organic resist underlayer film pattern for ion implantation formed by the three-layer resist method, since the substrate is not processed using the organic resist underlayer film pattern as a mask, actually, as described above, Silicon remains. Therefore, when ions are implanted using the organic resist underlayer film pattern as a shielding mask, silicon remaining on the organic resist underlayer film is denatured by ions injected, and in the cleaning process after the implantation process, Which can not be removed together and can not be removed remain as foreign matter on the substrate, resulting in a decrease in the yield of the ion implantation process. In order to prevent this, the silicon component remaining on the organic resist underlayer film pattern before ion implantation must be selectively cleaned and removed without affecting the organic resist underlayer film pattern. However, this silicon component is denatured by the dry etching gas at the time of pattern transfer to the organic resist underlayer film, and as a cleaning liquid which does not damage the substrate, a hydrogen peroxide-containing aqueous ammonia solution (hereinafter referred to as " ammonia & Can not be cleaned and removed. In order to thoroughly remove the denatured silicon component, it is necessary to apply a hydrofluoric acid-based cleaning solution. However, this cleaning solution also damages the surface of the semiconductor substrate, thereby lowering the yield in the above-mentioned processing step. Therefore, there is a demand for a method capable of removing silicon remaining on the organic resist underlayer film pattern after the pattern transfer to the organic resist underlayer film by dry etching is completed without damaging the substrate, and a material suitable therefor is required.

Japanese Patent Laid-Open Publication No. 2016-094612 (U.S. Patent Application Publication No. 2013/0337649 (A1))

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described problems, and it is an object of the present invention to provide a semiconductor device substrate and a removing solution which does not damage the organic resist underlayer film necessary for the patterning process, for example, a cleaning solution called SC1 (Standard Cleaner 1) It is an object of the present invention to provide a composition for forming an organic film which is capable of easily forming a wettable organic film together with a silicon residue residue modified by dry etching using an aqueous ammonia solution containing hydrogen peroxide.

In order to solve the above problems, the present invention provides a composition for forming an organic film, wherein the composition for forming an organic film is a polymer compound having at least one of repeating units represented by the following general formulas (1) to (4) And an organic solvent, wherein the total amount of at least one member selected from the group consisting of propylene glycol ester, ketone and lactone in the organic solvent is more than 30 wt% in the total organic solvent.

Wherein R ₁ is a hydrocarbon group having 1 to 19 carbon atoms, a halogen atom, an alkoxy group, a carboxyl group, a sulfo group, a methoxycarbonyl group, a hydroxyphenyl group or an amino group, R ₂ is a hydrogen atom or AL, R ₃ is a hydrogen atom, a furanyl group, or a hydrocarbon group having 1 to 16 carbon atoms, which may have a chlorine atom or a nitro group, k ₁ , k ₂ and k ₃ are each a group capable of forming an acidic functional group 2, l is 1 to 3, m is 0 to 3, and n is 0 or 1.)

Such a composition for forming an organic film can be produced by using a semiconductor device substrate or a stripper solution which does not damage the underlying organic resist film layer required for the patterning process, for example, an ammonia aqueous solution containing hydrogen peroxide commonly called SC1, A composition for forming an organic film which can easily form a wet-removable organic film together with the silicon residue remaining after the etching. Such a composition for forming an organic film can be applied as a material for an ion-implanted shielding mask at the time of forming a three-dimensional transistor.

At this time, it is preferable that the organic film forming composition is to form an organic film to be introduced immediately below the silicon-containing resist intermediate film soluble in ammonia and water, and immediately above the organic resist underlayer film which is insoluble in ammonia and water.

The composition for forming an organic film of the present invention is an organic film formed between a lower layer film of an organic resist and a silicon-containing resist intermediate film formed immediately below the photoresist in a three-layer resist method formed on a substrate ) (Hereinafter also referred to as the present composition), and is a composition for forming an organic film capable of forming a substantially four-layer resist. A step of forming an organic resist underlayer film on the substrate, forming the organic film between the organic resist underlayer film and the silicon-containing resist interlayer film, then forming a silicon-containing resist interlayer film, further forming an upper resist layer, The pattern is transferred to the silicon-containing resist intermediate film by dry etching, and the organic film and the organic resist lower layer film are subjected to pattern transfer by dry etching using the transferred pattern as a mask. If the silicon-containing resist intermediate film is soluble in ammonia and water and the organic resist undercoat film is insoluble in ammonia and water, the silicon content remaining on the transferred pattern as described above is removed together with the organic film with ammonia and water Thus, an organic resist underlayer film pattern free of silicon residue can be obtained. When this organic resist underlayer film pattern is used as an ion implantation shielding mask, accurate ion implantation is possible even in a three-dimensional transistor having a large step, and a three-dimensional transistor can be processed with a high yield.

Further, at this time, it is preferable that the silicon-containing resist intermediate film contains either or both of boron and phosphorus.

When pattern transfer is uniformly performed on the organic film and the organic resist underlayer film by dry etching using the patterned silicon-containing resist interlayer film as a mask, the silicon-containing resist interlayer film pattern undergoes a structural change due to the action of gas or plasma during dry etching, The solubility in ammonia and water may be lowered. However, when the silicon-containing resist intermediate film contains either or both of boron and phosphorus, the silicon-containing resist interlayer and / or the silicon residue can be used as the silicon-containing resist intermediate film which is soluble in ammonia and water even after the dry etching, have.

In this case, it is preferable that the composition for forming an organic film further contains one or both of a thermal acid generator and a crosslinking agent.

If the organic film forming composition of the present invention contains either or both of a thermal acid generator and a crosslinking agent, it is possible not only to form an organic film having a uniform composition with a uniform film thickness on the organic resist underlayer film, Intermixing can be suppressed from occurring when the silicon-containing resist intermediate film is formed on the film.

At this time, the organic film-forming composition was spin-coated on the substrate and then heated to be treated with a solution at 65 占 폚 mixed with 29% ammonia water / 35% hydrogen peroxide solution / water = 1 / It is desirable to provide an organic film having a dissolution rate of 5 nm / min or more.

If the organic film-forming composition provides an organic film having such a performance, it is possible to sufficiently remove the ammonia and water-based organic film and the silicon residue on the organic film without damaging the substrate for semiconductor device production.

Further, it is preferable that the organic film forming composition provides an organic film having a film thickness of 10 nm or more and less than 100 nm.

If the organic film-forming composition provides an organic film having such a film thickness, even if the silicon-containing resist intermediate film is used as a dry etching mask to pattern transfer the organic film and the organic resist underlayer film, It is possible to transfer the pattern in a state of being maintained.

Such a composition for forming an organic film can be used for a semiconductor device substrate or a stripping solution which does not cause damage to the organic resist underlayer film required for the patterning process, for example, a semiconductor device which is denatured by dry etching using ammonia and water commonly called SC1, Which is capable of easily forming a wet-removable organic film together with the silicon residue residue. Further, by applying the composition for forming an organic film of the present invention between the organic resist underlayer film and the silicon-containing resist interlayer, it is possible to form an ion implantation mask in which the silicon content remains on the pattern at the time of forming the shielding mask for ion implantation . As a result, it is possible to prevent a reduction in the yield in the manufacturing process of the three-dimensional transistor, and it becomes possible to economically manufacture a higher-performance semiconductor device.

As described above, a semiconductor device substrate or a removing solution which does not cause damage to the organic resist underlayer film required in the patterning process, for example, a silicon component denatured by dry etching using ammonia and water, which is generally used in a semiconductor manufacturing process, There is a demand for a composition for forming an organic film capable of easily forming a wet-removable organic film together with a residue.

As a result of intensive studies on the above problems, the inventors of the present invention have found that a polymer comprising a polymer having at least one of the repeating units represented by the following general formulas (1) to (4) and an organic solvent, , It is found that the above problems can be solved if the total amount of at least one selected from propylene glycol ester, ketone, and lactone is in the amount of more than 30 wt% in the total organic solvent. .

That is, the present invention provides a composition for forming an organic film, wherein the composition for forming an organic film contains an organic solvent and a polymer compound having any one or more of repeating units represented by the following general formulas (1) to (4) , And the total amount of at least one selected from propylene glycol ester, ketone and lactone in the organic solvent is more than 30 wt% in the total organic solvent.

Wherein R ₁ is a hydrocarbon group having 1 to 19 carbon atoms, a halogen atom, an alkoxy group, a carboxyl group, a sulfo group, a methoxycarbonyl group, a hydroxyphenyl group or an amino group, R ₂ is a hydrogen atom or AL, R ₃ is a hydrogen atom, a furanyl group, or a hydrocarbon group having 1 to 16 carbon atoms, which may have a chlorine atom or a nitro group, k ₁ , k ₂ and k ₃ are each a group capable of forming an acidic functional group 2, l is 1 to 3, m is 0 to 3, and n is 0 or 1.)

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

[Composition for forming organic film]

The composition for forming an organic film of the present invention comprises a polymer compound and an organic solvent. Hereinafter, each component will be described in further detail.

≪ Polymer compound &

The polymer compound in the composition for forming an organic film of the present invention has any one or more of repeating units represented by the following general formulas (1) to (4).

Wherein R ₁ is a hydrocarbon group having 1 to 19 carbon atoms, a halogen atom, an alkoxy group, a carboxyl group, a sulfo group, a methoxycarbonyl group, a hydroxyphenyl group or an amino group, R ₂ is a hydrogen atom or AL, R ₃ is a hydrogen atom, a furanyl group, or a hydrocarbon group having 1 to 16 carbon atoms, which may have a chlorine atom or a nitro group, k ₁ , k ₂ and k ₃ are each a group capable of forming an acidic functional group 2, l is 1 to 3, m is 0 to 3, and n is 0 or 1.)

Here, examples of the repeating unit represented by the general formula (1) include those having the following structures.

As the repeating unit represented by the general formula (2), those having the following structures can be exemplified.

As the repeating unit represented by the general formula (3), those having the following structures can be exemplified.

As the repeating unit represented by the general formula (4), those having the following structures can be exemplified.

Among them, preferred examples of the repeating unit include those represented by the above general formula (2) or (3). When a composition for forming an organic film containing a polymer compound having such a repeating unit is used, an organic film having excellent wet-removing properties by ammonia and water can be formed by effectively positioning a carboxyl group having a high polarity.

Examples of the monomer for obtaining n = 0 as the repeating unit represented by the general formulas (1) to (4) include phenol, o-cresol, m-cresol, p-cresol, 2,3- Dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5- Butylphenol, 4-t-butylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, Propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-t-butylphenol, 3-methoxyphenol, Methylphenol, 2-t-butyl-5-methylphenol, 4-phenylphenol, tritylphenol, pyrogallol, thymol, hydroxyphenylglycidyl ether, 4- 4-chlorophenol, 4-hydroxybenzenesulfonic acid, 4-vinylphenol, 1- (4-chlorophenol, De-hydroxy phenyl) naphthalene and the like.

Examples of the monomer for obtaining n = 1 include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 5-amino-1-naphthol, 2-methoxycarbonyl- Naphthol, 6'-B2,2'-naphthol, 6- (4-hydroxyphenyl) -2-naphthol, 6- Naphthol, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 6-hydroxy-2-vinylnaphthalene, 1-hydroxymethylnaphthalene, 2-hydroxymethylnaphthalene, Sulfonic acid, 2-hydroxynaphthalene-7-sulfonic acid, 2,3-dihydroxynaphthalene-7-sulfonic acid, and 1,7-dihydroxynaphthalene-3-sulfonic acid .

These may be used alone or in combination of two or more in order to control the n-value, the k-value and the etching resistance.

As the condensing agent for condensation reaction with these monomers, the following aldehyde compounds can be mentioned. For example, there may be mentioned aliphatic hydrocarbons such as formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, cyclopentanecarboxyaldehyde, cyclopentenecarboxyaldehyde, cyclohexanecarboxyaldehyde, cyclohexenecarboxyaldehyde, norbornane carboxyaldehyde, Aldehyde, adamantanecarbaldehyde, benzaldehyde, phenylacetaldehyde,? -Phenylpropylaldehyde,? -Phenylpropylaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-di Benzylaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4- dihydroxybenzaldehyde, 2- chlorobenzaldehyde, 3- chlorobenzaldehyde, Benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenz Benzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, anthracene carbaldehyde, pyrenecarboaldehyde, furfural and the like can be used in combination with a base such as benzylaldehyde, 2-ethylbenzaldehyde, .

Other compounds that can be represented by the following formulas can be exemplified.

The ratio of the monomer and the aldehyde compound as a condensing agent is preferably 0.01 to 5 mol, more preferably 0.05 to 2 mol, based on 1 mol of the total amount of the monomers.

The proportion of the total repeating units in the repeating units represented by the general formulas (1) to (4) is preferably not less than 10%, more preferably not less than 30%, as 100% as a whole.

When the polycondensation reaction is carried out using such a raw material as described above, the reaction can be carried out usually at room temperature or under cooling or heating as required, using an acid or a base as a catalyst in the absence of a solvent or a solvent, Can be obtained. Examples of the solvent to be used include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether Ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and 1,4-dioxane, methylene chloride, chloroform, dichloroethane and trichlorethylene Chlorinated solvents, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene, nitriles such as acetonitrile, ketones such as acetone, ethylmethylketone and isobutylmethylketone, ethylacetate, Propylene glycol methyl ether acetate and the like, lactones such as? -Butyrolactone, dimethylsulfoxide, N, N-dimethylformamide, hexamethylphosphoric acid And protonic polar solvents such as pyridinium chloride, pyridinium chloride, and rhodamine. These solvents may be used singly or in combination of two or more. These solvents may be used in the range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw material.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and heteropoly acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid and trifluoromethanesulfonic acid, Aluminum, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride Lewis acids such as titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide and titanium oxide can be used. Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride and calcium hydride; Alkylamines such as ethylmagnesium bromide, alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, organic bases such as triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, And organic bases such as pyridine. The amount to be used is preferably 0.001 to 100% by weight, more preferably 0.005 to 50% by weight based on the raw material. The reaction temperature is preferably from -50 deg. C to the boiling point of the solvent, more preferably from room temperature to 100 deg.

Examples of the method of the polycondensation reaction include a method of collecting monomers, a condensing agent and a catalyst, and a method of dropping a monomer and a condensing agent in the presence of a catalyst.

After completion of the polycondensation reaction, a method of removing volatile components in an amount of about 1 to 50 mmHg by raising the temperature of the reactor to 130 to 230 ° C in order to remove unreacted raw materials, catalysts, and the like existing in the system, A method in which water is added to fractionate the polymer, a method in which the polymer is dissolved in a good solvent, and a method in which the polymer is reprecipitated in a poor solvent can be used depending on the properties of the obtained reaction products.

The molecular weight of the thus obtained polymer in terms of polystyrene is preferably 500 to 500,000, more preferably 1,000 to 100,000, in terms of weight average molecular weight (Mw). The degree of dispersion of the molecular weight is preferably in the range of 1.2 to 20. By cutting a monomer component, an oligomer component, or a low molecular weight substance having a molecular weight (Mw) of 1,000 or less, the volatile components in the baking can be suppressed, and the contamination around the baking cup or the surface defects due to the dropped volatile components falling on the wafer can be prevented .

<Organic solvent>

The composition for forming an organic film of the present invention includes an organic solvent. Specific examples of the organic solvent include ketones such as cyclopentanone, cyclohexanone and methyl-2-amyl ketone, ketones such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy- Alcohols such as ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether and ethylene glycol monoethyl ether, ethers such as propylene glycol dimethyl ether and diethylene glycol dimethyl ether Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, Mono tert-butyl ether acetate and the like, and? -Butyrolactone, and they may be used singly or in combination of two or more. But are not limited to these.

Here, in the organic solvent, at least one selected from the group consisting of propylene glycol ester, ketone and lactone (for example, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, methyl-2-amyl Ketone, and? -Butyrolactone) must occupy more than 30 wt% of the total organic solvent. If the organic solvent does not satisfy this condition, a homogeneous organic film can not be formed directly on the undercoat layer of the organic resist.

In the composition for forming an organic film of the present invention, an acid generator or a crosslinking agent may be added to further promote the crosslinking reaction. Examples of the acid generator include those which generate an acid by thermal decomposition (a thermal acid generator) and those which generate an acid upon irradiation of light, any of which can be added.

Examples of the acid generator include an onium salt, a diazomethane derivative, a glyoxime derivative, a bisulfone derivative, a sulfonic acid ester of an N-hydroxyimide compound, a? -Ketosulfonic acid derivative, a disulfone derivative, a nitrobenzylsulfonate derivative, Sulfonic acid ester derivatives and the like. Specifically, those described in paragraphs (0081) to (0111) of Japanese Patent Application Laid-Open No. 2008-65303 (specification of U.S. Patent Application Publication No. 2008/0038662 (A1)).

Examples of the crosslinking agent include a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, a guanamine compound, a glycoluril compound or a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, And a compound containing a double bond such as a vinyl ether group or a vinyl ether group. Specifically, those described in paragraphs (0074) to (0080) of Japanese Patent Application Laid-Open No. 2008-65303 (specification of United States Patent Application Publication No. 2008/0038662 (A1)).

Further, a surfactant may be added to the composition for forming an organic film of the present invention in order to improve the coating property in spin coating. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, A fluorinated surfactant, and a surfactant of a partially fluorinated oxetane ring-opening polymer system. Specifically, those described in paragraphs (0142) to (0147) of Japanese Patent Application Laid-Open No. 2009-269953 (specification of United States Patent Application Publication No. 2009/0274978 (A1)).

Further, a basic compound for improving storage stability may be added to the composition for forming an organic film of the present invention. The basic compound serves as a quencher for an acid to prevent an acid generated in a smaller amount than the acid generator from proceeding the crosslinking reaction. Examples of such basic compounds include nitrogen-containing compounds having primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxyl groups, sulfonyl groups having sulfonyl groups, A nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like. Specifically, those described in paragraphs (0112) to (0119) of Japanese Patent Application Laid-Open No. 2008-65303 (specification of United States Patent Application Publication No. 2008/0038662 (A1)).

The organic film forming composition of the present invention as described above can be suitably used for forming an organic film immediately below the silicon-containing resist intermediate film soluble in ammonia and water and immediately above the organic resist underlayer film which is resistant to ammonia and water.

The organic film forming composition of the present invention preferably provides an organic film having a film thickness of 10 nm or more and less than 100 nm, more preferably 20 nm or more and 80 nm or less. If the film thickness of the organic film is 10 nm or more, the effect of removing the silicon component by the wet process can be sufficiently obtained. If the film thickness is less than 100 nm, side etching during dry etching can be suppressed, do.

[Organic film]

An organic film can be formed by the composition for forming an organic film of the present invention. Examples of the method for forming an organic film using the composition for forming an organic film of the present invention include a method of coating the above-mentioned composition for forming an organic film of the present invention on a substrate to be processed by a spin coating method or the like. After the spin-coating, the solvent is evaporated, and baking is performed to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film and the resist interlayer film. The baking is performed in a range of 100 ° C or higher and 400 ° C or lower, and is performed within a range of 10 to 600 seconds, preferably 10 to 300 seconds. The baking temperature is more preferably 150 ° C or higher and 350 ° C or lower.

As described above, the organic film formed by the composition for forming an organic film of the present invention can be suitably introduced directly below the silicon-containing resist intermediate film and also over the organic resist underlayer film.

Such a silicon-containing resist intermediate film is preferably soluble in ammonia and water and capable of dissolving or exfoliating with ammonia and water. For example, Japanese Patent Application Laid-Open No. 2010-085912 (specification of U.S. Patent Application Publication No. 2010/0086870 (A1)), Japanese Patent Application Publication No. 2010-085893 (specification of U.S. Patent Application Publication No. 2010/0086872 (A1) Japanese Patent Laid-Open Publication No. 2015-028145 (specification of U.S. Patent Application Publication No. 2015/0004791 (A1)), International Publication No. 2010/068336 (U.S. Patent Application Publication No. 2011/0233489 (A1) The silicon-containing resist layer described in the specification of International Patent Application Publication No. 2016-074772 (specification of U.S. Patent Application Publication No. 2016/0096977 (A1)) and Japanese Patent Laid-Open Publication No. 2016-074774 (specification of U.S. Patent Application Publication No. 2016/0096978 (A1) It is preferable to use the film as the silicon-containing resist intermediate film in the present invention. Among these, it is particularly preferable to include either or both of boron and phosphorus because of their excellent wet-removing ability by ammonia and water.

As the organic resist underlayer film applicable to the present invention, those having resistance to ammonia and water (that is, those resistant to ammonia and water) are preferable. For example, Japanese Patent Application Laid-Open No. 2004-205685 (US Patent No. 7,427,464 (B2)), Japanese Patent Application Laid-Open No. 2010-122656 (US Patent Application Publication No. 2010/0099044 (A1) (Japanese Patent Application Laid-Open Publication No. Hei 0184404 (A1)), Japanese Patent Application Laid-Open Publication No. 2012-214720 (U.S. Patent Application Publication No. 2012/0252218 A1), Japanese Laid-Open Patent Application No. 2016-094612 (U.S. Patent Application Publication No. 2013/0337649 (A1)) can be used.

The above-described organic resist underlayer film is formed by coating an organic resist underlayer film composition on a substrate to be processed by spin coating or the like. By using the spin coat method or the like, good embedding characteristics can be obtained. After the spin-coating, the solvent is evaporated and baking is carried out to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film and the resist interlayer film. The baking is performed at a temperature of 100 ° C or higher and 600 ° C or lower, and is performed within a range of 10 to 600 seconds, preferably 10 to 300 seconds. The baking temperature is more preferably 200 DEG C or more and 500 DEG C or less. Considering the effect on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600 占 폚 or lower, and more preferably 500 占 폚 or lower.

As described above, in the method of forming the organic resist underlayer film, the organic resist underlayer film composition is coated on the substrate to be processed by spin coating or the like, and the composition is baked in air, N ₂ , Ar, To thereby form an organic resist underlayer film. By firing the organic resist underlayer film composition in an atmosphere containing oxygen, a cured film resistant to ammonia and water can be obtained.

By forming the organic resist underlayer film in this manner, a flat cured film can be obtained regardless of the irregularities of the substrate to be processed by its excellent embedding / planarizing property. Therefore, a flat cured film is formed on a substrate having a height of 30 nm or more, It is very useful when it is formed.

The thickness of the organic resist underlayer film for planarizing and manufacturing semiconductor devices is appropriately selected, and is preferably 5 to 500 nm, particularly 10 to 400 nm.

When the composition for forming an organic film of the present invention is applied to the formation of an organic film which is directly under the silicon-containing resist intermediate film and immediately above the organic resist underlayer film and the mask for ion implantation is formed, In order to wet-remove the intermediate film containing resist, a peeling solution containing hydrogen peroxide is preferable. At this time, in order to promote peeling, it is more preferable to adjust the pH by adding an acid or an alkali to the peeling solution. Examples of such a pH adjuster (acid or alkali) include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, oxalic acid, tartaric acid, citric acid and lactic acid, alkali containing nitrogen such as ammonia, ethanolamine, tetramethylammonium hydroxide, EDTA Diamine tetraacetic acid), and the like, and the like. Ammonia is particularly preferred. That is, as the exfoliation liquid, ammonia and the like are preferable.

When ammonia and water are used as the exfoliation liquid, the ratio of ammonia to hydrogen peroxide and dilution deionized water is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and more preferably 0.05 to 15 parts by mass, relative to 100 parts by mass of deionized water 0.1 to 10 parts by mass, and the hydrogen peroxide is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass.

For the wet removal, a release liquid having a temperature of 0 ° C to 80 ° C, preferably 5 ° C to 70 ° C is prepared, and a silicon wafer having a processed substrate to be processed is formed thereon. If necessary, the silicon-containing resist intermediate film and the organic film formed by the organic film forming composition of the present invention can be easily removed according to the procedure of the present invention, for example, by spraying a peeling liquid on the surface or by applying a peeling liquid while rotating the wafer have.

Particularly, the composition for forming an organic film of the present invention can be obtained by spin coating a substrate and then heating it to a treatment with a solution at 65 占 폚 mixed with 29% ammonia water / 35% hydrogen peroxide solution / water = 1 / It is desirable to provide an organic film having a dissolution rate of 5 nm / min or more.

It is also preferable to determine the degree of removal of silicon powder by quantifying silicon remaining on the surface of the lower layer film of the organic resist after ammonia and water treatment. For example, analysis can be performed by the method described in Japanese Patent Laid-Open Publication No. 2016-177262 (specification of U.S. Patent Application Publication No. 2016/0276152 (A1)).

As described above, the composition for forming an organic film of the present invention can be applied to a semiconductor device substrate and a removing solution which does not damage the organic resist underlayer film necessary for the patterning step, for example, ammonia and water called SC1, And is capable of forming a wettable organic film easily together with the silicon residue residue modified by dry etching. Further, by applying the composition for forming an organic film of the present invention between the organic resist underlayer film and the silicon-containing resist interlayer, it is possible to form an ion implantation mask in which the silicon content remains on the pattern at the time of forming the shielding mask for ion implantation . As a result, it is possible to prevent a reduction in the yield in the manufacturing process of the three-dimensional transistor, and it becomes possible to economically manufacture a higher performance semiconductor device.

Example

Hereinafter, the present invention will be described in detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples,% represents mass% and molecular weight was measured by GPC. In the GPC measurement, the detection was performed by RI, and the elution solvent was tetrahydrofuran, and the molecular weight in terms of polystyrene was determined.

[Synthesis of Polymer Compound]

[Synthesis Example (A1)]

40.00 g (0.36 mol) of resorcinol, 10.00 g of a 20 mass% PGME solution of p-toluenesulfonic acid monohydrate and 72.00 g of 2-methoxy-1-propanol were placed in a 500 ml three-necked flask, And heated. 23.59 g of 37% formalin (0.29 mol of formaldehyde) was added thereto, followed by stirring for 11 hours. 160 g of ultrapure water and 200 g of ethyl acetate were added to the reaction solution, transferred to a separating funnel, and washed 10 times with 150 g of ultrapure water to remove the acid catalyst and metal impurities. The obtained organic layer was concentrated under reduced pressure to 76 g, and ethyl acetate was added to make 150 g of a solution, and 217 g of n-hexane was added. the n-hexane layer was separated into the upper layer and the high-concentration polymer solution was separated into the lower layer, and this upper layer was removed. The same operation was repeated twice, and the obtained polymer solution was concentrated and dried under reduced pressure at 80 DEG C for 13 hours to obtain a polymeric compound A1. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 800 and Mw / Mn = 1.3. This polymer compound A1 has a repeating unit represented by the general formula (4).

[Synthesis Example (A2)]

80.1 g (0.50 mol) of 1,5-dihydroxynaphthalene, 26.4 g (0.24 mol) of a 37% formalin solution and 250 g of 2-methoxy-1-propanol were placed in a 1,000 ml three- , 18 g of 20% para-toluenesulfonic acid 2-methoxy-1-propanol solution was added slowly, and the mixture was stirred at a liquid temperature of 110 ° C for 12 hours. After cooling to room temperature, 500 g of methyl isobutyl ketone was added, and the organic layer was washed five times with 200 g of pure water, and the organic layer was dried under reduced pressure. 300 mL of THF was added to the residue, and the polymer was reprecipitated with 2,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A2. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 3,000 and Mw / Mn = 2.7. This polymer compound A2 has a repeating unit represented by the general formula (4).

[Synthesis Example (A3)]

A 2,000 ml three-necked flask was charged with 80.1 g (0.50 mol) of 1,5-dihydroxynaphthalene, 100.1 g (0.40 mol) of 3,4-di-t-butoxybenzaldehyde and 600 g of 2-methoxy- Was made a uniform solution at a liquid temperature of 80 占 폚 in a nitrogen atmosphere, and then 6.4 g of a 25% aqueous solution of sodium hydroxide was slowly added thereto, followed by stirring at a liquid temperature of 110 占 폚 for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A3. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 2,900 and Mw / Mn = 2.9. This polymer compound A3 has a repeating unit represented by the general formula (1).

[Synthesis Example (A4)]

80 g (0.50 mol) of 1,5-dihydroxynaphthalene, 36.6 g (0.30 mol) of 4-hydroxybenzaldehyde and 145 g of methyl cellosolve were added to a 1,000-mL flask, and while stirring at 70 캜, p-toluenesulfonic acid 20 g of a 20% by mass methylcellosolve solution was added. The temperature was raised to 85 DEG C and the mixture was stirred for 6 hours, then cooled to room temperature, and diluted with 800 mL of ethyl acetate. Transferred to a separatory funnel, and washed with 200 mL of deionized water to remove the reaction catalyst and metal impurities. After the obtained solution was concentrated under reduced pressure, 600 mL of ethyl acetate was added to the residue, and the polymer was precipitated with 2,400 mL of hexane. The precipitated polymer was separated by filtration, recovered, and dried under reduced pressure to obtain a polymer compound A4. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 3,800 and Mw / Mn = 2.4. This Polymer Compound A4 has a repeating unit represented by the general formula (1).

[Synthesis Example (A5)]

80.1 g (0.50 mol) of 2,7-dihydroxynaphthalene, 100.1 g (0.40 mol) of terephthalaldehyde in t-butyl and 600 g of 2-methoxy-1-propanol were placed in a 2,000 ml three- After the solution was made into a homogeneous solution at a liquid temperature of 80 캜, 6.4 g of a 25% aqueous solution of sodium hydroxide was added slowly, and the mixture was stirred at a liquid temperature of 110 캜 for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A5. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 2,900 and Mw / Mn = 2.9. This polymer compound A5 has a repeating unit represented by the general formula (2).

[Synthesis Example (A6)]

94.4 g (0.50 mol) of 6-hydroxy-2-naphthoic acid, 100.1 g (0.40 mol) of terephthalaldehyde acid and 600 g of 2-methoxy- , 6.4 g of a 25% sodium hydroxide aqueous solution was added slowly, and the mixture was stirred at a liquid temperature of 110 占 폚 for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A6. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 3,500 and Mw / Mn = 2.8. This polymer compound A6 has a repeating unit represented by the general formula (2).

[Synthesis Example (A7)]

80.1 g (0.50 mol) of 1,5-dihydroxynaphthalene, 60.1 g (0.40 mol) of terephthalaldehyde acid and 600 g of 2-methoxy-1-propanol were placed in a 2,000 ml three-necked flask under a nitrogen atmosphere at a temperature of 80 ° C After the mixture was made into a homogeneous solution, 6.4 g of a 25% aqueous solution of sodium hydroxide was added slowly, and the mixture was stirred at a liquid temperature of 110 ° C for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A7. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 2,200 and Mw / Mn = 2.9. This polymer compound A7 has a repeating unit represented by the general formula (2).

[Synthesis Example (A8)]

9.4 g (0.05 mol) of 6-hydroxy-2-naphthoic acid, 5.3 g (0.05 mol) of terephthalaldehyde acid and 60 g of 2-methoxy-1-propanol were placed in a 200 ml three- , 0.6 g of a 25% aqueous sodium hydroxide solution was added slowly, and the mixture was stirred at a liquid temperature of 110 占 폚 for 24 hours. After cooling to room temperature, 150 g of ethyl acetate was added, and the organic layer was washed with 30 g of a 3% nitric acid aqueous solution, further washed five times with 30 g of pure water, and dried under reduced pressure. 40 mL of THF was added to the residue, and the polymer was reprecipitated with 300 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A8. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 2,000 and Mw / Mn = 2.6. This Polymer Compound A8 has a repeating unit represented by the general formula (2).

[Synthesis Example (A9)]

Into a 2,000 ml three-necked flask, 54.1 g (0.50 mol) of o-cresol, 140.2 g (0.40 mol) of 3,4-bis (t-butoxycarbonylmethoxy) benzaldehyde and 600 g of 2-methoxy- Was made a uniform solution at a liquid temperature of 80 占 폚 in a nitrogen atmosphere, and then 6.4 g of a 25% aqueous solution of sodium hydroxide was slowly added thereto, followed by stirring at a liquid temperature of 110 占 폚 for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A9. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 3,200 and Mw / Mn = 3.0. This polymer compound A9 has a repeating unit represented by the general formula (3).

[Synthesis Example (A10)]

A 2,000 ml three-necked flask was charged with 80.1 g (0.50 mol) of 1,6-dihydroxynaphthalene, 94.5 g (0.40 mol) of 4-t-butoxycarbonylmethoxybenzaldehyde and 600 g of 2-methoxy- Was made a uniform solution at a liquid temperature of 80 占 폚 in a nitrogen atmosphere, and then 6.4 g of a 25% aqueous solution of sodium hydroxide was slowly added thereto, followed by stirring at a liquid temperature of 110 占 폚 for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, and the organic layer was washed with 300 g of 3% nitric acid aqueous solution, followed by washing with 300 g of pure water five times, followed by drying under reduced pressure. 400 mL of THF was added to the residue, and the polymer was reprecipitated with 3,000 mL of hexane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain Polymer Compound A10. The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC to find that Mw = 2,700 and Mw / Mn = 2.7. This polymer compound A10 has a repeating unit represented by the general formula (3).

[Examples and Comparative Examples]

0.1% by mass of the above-mentioned polymeric compounds A1 to A10, crosslinking agents XL1 to XL3 as additives, a thermal acid generator AG1 and FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) as a surfactant were mixed in the ratios shown in Table 1 (Sol. 1 to 19) were respectively prepared by filtration through a filter made of a fluororesin of 0.1 mu m. Here, Sol. 1 to 10 and 17 to 19 are the composition for forming an organic film of the present invention, and Sol. 11 to 16 are comparative organic film forming compositions. Table 1 also shows the amount of at least one selected from propylene glycol ester, ketone and lactone in the total amount of the organic solvent in the composition for forming an organic film.

Hereinafter, the thermal acid generator AG1 and crosslinking agents XL1 to XL3 are shown.

In Table 1, the organic solvent means the following.

PGMEA: Propylene glycol methyl ether acetate

Cyho: Cyclohexanone

PGEE: Propylene glycol ethyl ether

GBL:? -Butyrolactone

4M2P: 4-methyl-2-pentanol

[Solvent resistance evaluation: Examples 1-1 to 13 and Comparative Examples 1-1 to 6]

The organic film formed by the composition for forming an organic film of the present invention was spin-coated on the silicon-containing resist intermediate film immediately thereon. Therefore, in order to investigate whether the organic film to be formed was an organic film that did not intermix, resistance to an organic solvent was evaluated . Each of the compositions for forming an organic film (Sol. 1 to 19) described above was coated on a silicon substrate and baked at 285 DEG C for 60 seconds to form an organic film, and the film thickness T1 was measured. PGMEA / PGME = 30/70 (mass ratio) was spin-coated on the obtained organic film, and then heat treatment was performed at 100 占 폚 for 30 seconds to measure the film thickness T2. From these measurement results, the film thickness decrease represented by T1-T2 was calculated. The results are shown in Table 2.

As shown in Examples 1-1 to 13 of Table 2, Sol. 1 to 10, and 17 to 19 have sufficient organic solvent resistance. Thus, it has become clear that even when the silicon-containing resist intermediate film is spin-coated directly on these organic films, a laminated film can be formed without intermixing.

[Evaluation of film formability on organic resist underlayer films: Examples 2-1 to 13 and Comparative Examples 2-1 to 6]

Since the organic film formed by the organic film-forming composition of the present invention is laminated on the organic resist underlayer film, the film-forming property on the organic resist underlayer film is confirmed. On the silicon wafer, a spin-on-carbon film ODL-102 manufactured by Shin-Etsu Chemical Co., Ltd. was applied as an organic resist undercoat film to form an organic resist undercoat film having a film thickness of 200 nm. Organic film forming compositions (Sol. 1-19) were coated thereon and baked at 285 캜 for 60 seconds to form an organic film, and the film formation state of the organic film was confirmed. The results are shown in Table 3.

As shown in Examples 2-1 to 13 of Table 3, Sol. 1 to 10 and 17 to 19, it was possible to form a film on the organic resist underlayer film by a spin coat without defective deposition. On the other hand, as shown in Comparative Examples 2-1 to 6-6, the sol containing 70 wt% or more of an alcohol-based organic solvent. 11 to 16 were skewed on the organic resist underlayer film, and the films could not be laminated.

[Wet removability by ammonia and water in organic film: Examples 3-1 to 10]

Each of the compositions for forming an organic film (Sol. 1 to 10) was coated on a silicon substrate and baked at 285 DEG C for 60 seconds to form an organic film having a thickness of 25 nm to measure a film thickness T1. This membrane was mixed with 29% ammonia water / 35% hydrogen peroxide solution / water = 1/1/8 and immersed in ammonia and water kept at 65 ° C for 5 minutes, washed with pure water and then heated and dried at 100 ° C for 60 seconds, T3 was measured. The film removal rate at this time was also determined. The results are shown in Table 4.

As shown in Table 4, it was found that the organic film formed with Sol.1 to 10 can be removed at a rate of 5 nm / min or more with ammonia and water.

[Residue evaluation after organic resist underlayer film ashing: Examples 4-1 to 13, Comparative Example 4-1]

On the silicon wafer, a spin-on-carbon film ODL-102 manufactured by Shin-Etsu Chemical Co., Ltd. was formed to a film thickness of 200 nm as an organic resist undercoat film. Organic film forming compositions (Sol. 1 to 10, 17 to 19) of the present invention were applied to the substrate and heated at 285 캜 for 60 seconds to laminate the organic film. On the other hand, in Comparative Example 4-1, no organic film was introduced.

Subsequently, a silicon-containing resist intermediate film forming composition (SiARC-1) shown in the following Table 5 was applied and heated at 220 캜 for 60 seconds to laminate a silicon-containing resist intermediate film having a film thickness of 35 nm. The positive type developing ArF resist solution (PR-1) shown in the following Table 6 was applied on the resist film, and heated at 110 DEG C for 60 seconds to form a photoresist film having a film thickness of 100 nm. Further, the liquid immersion passivation film composition (TC-1) shown in Table 7 below was coated on this photoresist film and heated at 90 캜 for 60 seconds to form a protective film having a thickness of 50 nm.

Subsequently, these wafers were exposed with an ArF liquid immersion exposure apparatus (NSR-S610C manufactured by Nikon Corporation, NA 1.30, σ0.98 / 0.65, 35 degrees dipole polarized illumination, 6% halftone phase shift mask) (PEB), and developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 160 nm 1: 1 positive line & space pattern. The thus obtained wafer was observed with the electron microscope (S-4800, manufactured by Hitachi, Ltd.) and the pattern was observed with the electron microscope (CG4000, manufactured by Hitachi High Technologies) did.

These wafers, from which a photoresist pattern was obtained, were subjected to dry etching under the processing conditions shown in Tables 8 and 9 by using a Tokyo Electron etching apparatus Telius to process a silicon-containing resist interlayer film and an organic resist underlayer film. In the obtained wafer, the cross-sectional shape of the pattern was observed with an electron microscope (S-9380, manufactured by Hitachi, Ltd.).

Subsequently, in order to wet-remove the silicon-containing resist intermediate film remaining after the organic resist underlayer film processing, the wafer was mixed with 29% ammonia water / 35% hydrogen peroxide solution / water = 1/1/8, Treated for 5 minutes. After the treatment, it was washed with pure water, and dried by heating at 100 DEG C for 60 seconds. In order to confirm whether or not the silicon component could be removed by ammonia and water treatment, the surface of the organic resist underlayer film was subjected to XPS analysis by K-ALPHA manufactured by Thermo Fisher Scientific Co., Ltd. to quantify silicon on the organic resist underlayer film did.

The organic resist underlayer film pattern obtained in the above process was treated under the treatment conditions shown in Table 10 using a Tokyo Electron etch apparatus Telius to remove the remaining organic resist underlayer film by ashing. The wafer after the ashing treatment was observed with an electron microscope (CG4000) manufactured by Hitachi, Ltd., and the presence or absence of the residue was confirmed. The results are shown in Table 11.

The composition of the silicon-containing resist intermediate film forming composition (SiARC-1) is shown in Table 5 below.

TPSNO ₃ : Triphenylsulfonium nitrate

The molecular weight and the structural formula of SiARC polymer 1 shown in Table 5 are shown below.

SiARC polymer 1: molecular weight (Mw) = 2,800

The molecular weight and structural formula of SiARC polymer 2 shown in Table 5 are shown below.

SiARC polymer 2: molecular weight (Mw) = 2,800

The composition of the above positive-working developing ArF resist solution (PR-1) is shown in Table 6 below.

The molecular weight, the degree of dispersion and the structural formula of the ArF resist polymer 1 shown in Table 6 are shown below.

ArF resist polymer 1: Molecular weight (Mw) = 7,800

Dispersion degree (Mw / Mn) = 1.78

The structural formula of the acid generator PAG1 shown in Table 6 is shown below.

The structure shown in Table 6 is shown below: Quencher.

The composition of the liquid immersion protecting film composition (TC-1) used for the patterning test by the positive development described above is shown in Table 7 below.

The molecular weight, the degree of dispersion and the structural formula of the protective film polymer shown in Table 7 are shown below.

Shielding polymer: Molecular weight (Mw) = 8,800

Dispersion degree (Mw / Mn) = 1.69

The dry etching conditions of the silicon-containing resist intermediate film are shown in Table 8 below.

Dry etching conditions of the organic resist underlayer film are shown in Table 9 below.

The ashing removal conditions of the organic resist underlayer film are shown in Table 10 below.

As a result of observation of the cross-sectional shape and pattern collapse of the photoresist pattern obtained in the residue evaluation after the organic resist lower layer film ashing as described above and the result of observation of the cross-sectional shape of the pattern after dry etching, And the presence or absence of residue after ashing the organic resist underlayer film pattern are shown in Table 11 below.

As shown in Table 11, it was confirmed that Sol. 1 to 10 was introduced, no silicon remained on the organic resist underlayer film after the ammonia and water treatment, and the residue did not occur after ashing the organic resist underlayer film pattern. When the influence of the film thickness of the organic film in Examples 4-11 to 13 and Comparative Example 4-1 was confirmed, as shown in Example 4-11, when the organic film was thin, the organic resist underlayer film after ammonia treatment No silicon residue remained on the surface, and no residue remained after ashing the organic resist underlayer film pattern. Further, as shown in Examples 4-13, when the film was thick, side etching was applied to the organic film portion at the time of dry etching, but no residue remained after ashing the organic resist underlayer film pattern. On the other hand, as shown in Comparative Example 4-1, when the organic film was not present, the removal effect of the silicon residue was not obtained, and the residue remained after ashing the organic resist underlayer film pattern.

From the above, it can be seen that, in the case of the composition for forming an organic film of the present invention, the composition for forming an organic film can be easily wet-processed together with the residue of a silicon compound denatured by dry etching using a semiconductor device substrate or a removing solution which does not cause damage to the organic resist underlayer film required for the patterning step A composition for forming an organic film which can form a removable organic film has become clear and can be applied as a material for an ion implantation shielding mask at the time of forming a three-dimensional transistor. In particular, it has become clear that by introducing an organic film with a film thickness of 10 nm or more and less than 100 nm, it is possible to more reliably construct a processing process in which no residue is generated. As a result, it is possible to prevent a reduction in the yield in the manufacturing process of the three-dimensional transistor, and it is possible to economically manufacture a higher performance semiconductor device.

The present invention is not limited to the above-described embodiment. The above embodiment is an example, and anything that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims (9)

A composition for forming an organic film,
Wherein the composition for forming an organic film contains a polymer compound having at least one of repeating units represented by the following general formulas (1) to (4) and an organic solvent, and in the organic solvent, a propylene glycol ester, And lactone in an amount of more than 30 wt% in the total organic solvent.

Wherein R ₁ is a hydrocarbon group having 1 to 19 carbon atoms, a halogen atom, an alkoxy group, a carboxy group, a sulfo group, a methoxycarbonyl group, a hydroxyphenyl group or an amino group, and R ₂ is a hydrogen atom or AL. AL is a group that causes acidic functional groups by heating or acid action. R ₃ is a hydrogen atom, a furanyl group, or a hydrocarbon group having 1 to 16 carbon atoms which may have a chlorine atom or a nitro group. k ₁ , k ₂ and k ₃ are 1 to 2, 1 is 1 to 3, m is 0 to 3, and n is 0 or 1. The organic film forming composition according to claim 1, wherein the composition for forming an organic film is for forming an organic film to be introduced immediately below a silicon-containing resist intermediate film soluble in ammonia and water, and immediately below an organic resist underlayer film insoluble in ammonia and water By weight based on the total weight of the composition. 3. The organic film-forming composition according to claim 2, wherein the silicon-containing resist intermediate film contains either or both of boron and phosphorus. The organic film-forming composition according to claim 1, wherein the organic film-forming composition further contains one or both of a thermal acid generator and a crosslinking agent. The organic film-forming composition according to claim 2, wherein the composition for forming an organic film further contains one or both of a thermal acid generator and a crosslinking agent. The organic film-forming composition according to claim 3, wherein the composition for forming an organic film further contains one or both of a thermal acid generator and a crosslinking agent. The organic film forming composition according to any one of claims 1 to 6, wherein the organic film forming composition is spin-coated on the substrate and then heated so as to form a film with a composition of 29% ammonia water / 35% hydrogen peroxide solution / water = Wherein the organic film has a dissolution rate of 5 nm / min or more by treatment with a solution at 65 占 폚. The organic film-forming composition according to any one of claims 1 to 6, wherein the organic film-forming composition provides an organic film having a film thickness of 10 nm or more and less than 100 nm. The composition for forming an organic film according to claim 7, wherein the composition for forming an organic film has a film thickness of 10 nm or more and less than 100 nm.