KR102051189B1 - Composition for forming organic film - Google Patents

Abstract

An object of the present invention is to dry-etch by using a peeling solution that does not damage an organic resist underlayer film required in a semiconductor device substrate or a patterning step, for example, an aqueous hydrogen peroxide-containing ammonia solution called SC1 commonly used in semiconductor manufacturing processes. It is to provide an organic film-forming composition capable of forming an organic film which can be easily wet-removed together with the modified silicon powder residue.
As a solution of the present invention, as the composition for forming an organic film, the composition for forming an organic film includes a polymer compound and an organic solvent having any one or more of repeating units represented by the following general formulas (1) to (4). In the organic solvent, a composition for forming an organic film is provided in which at least one total selected from propylene glycol esters, ketones, and lactones accounts for more than 30 wt% of the total organic solvent.

Description

Composition for organic film formation {COMPOSITION FOR FORMING ORGANIC FILM}

TECHNICAL FIELD This invention relates to the multilayer resist film material used when forming a wiring pattern in the board | substrate for semiconductor device manufacture. Specifically, It is related with the composition for organic film formation.

Conventionally, the miniaturization of the pattern size by shortening the wavelength of the light source in the lithography technique has led to the increase in the processing capability of the semiconductor device. However, in recent years, since the speed of shortening after ArF light sources has slowed down, there has been a demand for high performance of processing capability of semiconductor devices in place of miniaturization. As one of the methods, a semiconductor device having high processing capacity has been proposed in which a three-dimensional transistor that can operate at a higher speed than a planar transistor is disposed at a higher density. The board | substrate (henceforth a board | substrate) for manufacturing such a semiconductor device has a three-dimensional structure which went through the complicated step processing compared with the conventional board | substrate. Therefore, when the pattern formation is to be performed by the pattern formation method using the single layer photoresist applied in forming a conventional planar transistor, the photoresist film follows the step formed during substrate processing, and the step is formed on the surface of the photoresist film. Occurs, and as a result, a flat resist film cannot be obtained. As a result, when the photoresist is exposed and the pattern is formed, the focus cannot be accurately focused on the photoresist, and as a result, the yield of substrate processing decreases. New materials and methods are needed to prevent this.

One of the methods for solving such a problem is the multilayer resist method. In this method, a stepped substrate is planarized by an underlayer film having high planarization performance, and a photoresist film is formed on the planar film, whereby the margin of focus at the time of exposure is widened and the yield reduction in substrate processing can be prevented. In this method, when the lower layer film having the etching selectivity is selected for the upper photoresist film and the substrate, respectively, a pattern is formed on the upper layer film of the resist, and then the pattern is formed on the intermediate film by dry etching using the resist upper layer film pattern as a dry etching mask. The pattern can be transferred to the substrate to be processed by dry etching using the underlayer film as a dry etching mask.

As this multilayer resist method, the three-layer resist method which can be performed using the general resist composition used by the single layer resist method is common. For example, an organic resist underlayer film having high flatness and dry etching resistance sufficient for substrate processing is formed on the substrate, and a silicon-containing resist underlayer film is formed thereon as an intermediate film (hereinafter referred to as a silicon-containing resist intermediate film). A photoresist film is formed as a resist upper layer film. With respect to dry etching with fluorine-based gas plasma, since the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, the resist pattern can be transferred to the silicon-containing resist intermediate film by using dry etching with fluorine-based gas plasma. have. In the dry etching with an oxygen-based gas plasma, since the silicon-based resist intermediate film has a good etching selectivity with respect to the organic resist underlayer film, the silicon-containing resist intermediate film pattern is made of an organic resist underlayer by using dry etching with an oxygen-based gas plasma. Can be transferred to the membrane. According to this method, a pattern having a sufficient film thickness for directly processing a substrate to be processed is a composition for forming a resist upper layer film, which is difficult to form, or a composition for forming a resist upper layer film having insufficient dry etching resistance to process a substrate. Even if it is used, if the pattern can only be transferred to the silicon-containing film, the pattern of the organic resist underlayer film having dry etching resistance sufficient for processing can be obtained. Such a pattern transfer by dry etching does not cause a problem such as pattern collapse caused by friction with a developer during the development of a resist, so that an organic film pattern having a thickness sufficiently functioning as a dry etching mask even at a high aspect ratio can be obtained. You can get it. And by using the pattern of the organic resist underlayer film formed in this way as a dry etching mask, it becomes possible to transfer a pattern to the board | substrate which has a three-dimensional transistor structure with a complicated level | step difference. As mentioned above, as an organic resist underlayer film, many things are already known, such as what was described in patent document 1, for example.

In general, in the three-layer resist method, in order to stabilize the processing dimension, in the pattern transfer by dry etching to the organic resist underlayer film, it is necessary to leave a silicon-containing resist intermediate film on the organic resist underlayer film pattern. The remaining silicon powder is etched away by the dry etching gas for processing the substrate when the pattern is transferred to the substrate using the organic resist underlayer film pattern as a mask. Not left. Therefore, even if the organic resist underlayer film pattern remaining after the substrate processing is dry etched (ashed) or wet removed, the silicon powder does not remain as a residue on the substrate.

Thus, since the multilayer resist method is applicable also to the board | substrate with which big step | step is formed as a board | substrate processing method, it is used for extensive board | substrate processing. Therefore, using this feature, it is expected to be used as an ion implantation mask of an ion implantation process that is part of the three-dimensional transistor formation process. However, in the organic resist underlayer film pattern for ion implantation formed by the three-layer resist method, since the substrate processing is not performed using the organic resist underlayer film pattern as a mask, it is actually on the organic resist underlayer film pattern as described above. Silicon powder remains. Therefore, when ions are implanted using such an organic resist underlayer film pattern as a shielding mask, the silicon powder remaining on the organic resist underlayer film is denatured by the implanted ions. What cannot be removed together and what cannot be removed will remain as foreign matter on the substrate, causing a decrease in the yield of the ion implantation step. In order to prevent this, the silicon powder remaining on the organic resist underlayer film pattern must be selectively washed and removed without affecting the organic resist underlayer film pattern before ion implantation. However, this silicon powder is denatured by dry etching gas when the pattern is transferred to the organic resist underlayer film, and it is a cleaning solution which does not damage the substrate. Also called water) can not be removed. In order to completely wash away the denatured silicon powder, application of a hydrofluoric acid-based cleaning liquid is required. However, the cleaning liquid also damages the surface of the semiconductor substrate, and the yield in the processing step is lowered. Then, after the pattern transfer to the organic resist underlayer film by dry etching is complete | finished, the method of removing the silicon powder which remained on the organic resist underlayer film pattern without damaging a board | substrate, and the material suitable for it are calculated | required.

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

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and is called a peeling liquid which does not damage an organic resist underlayer film required in a semiconductor device substrate or a patterning process, for example, SC1 (Standard Cleaner 1) commonly used in a semiconductor manufacturing process. An object of the present invention is to provide a composition for forming an organic film which can form an easily wet-removable organic film together with a silicon powder residue modified by dry etching using a hydrogen peroxide-containing ammonia aqueous solution.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, in this invention, the high molecular compound which has any 1 or more types of repeating units represented by following General formula (1)-(4) as said composition for organic film formation is represented. And an organic solvent, wherein in the organic solvent, at least one total selected from propylene glycol esters, ketones, and lactones comprises more than 30 wt% of the total organic solvent.

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

With such an organic film-forming composition, dry using a peeling solution that does not damage the organic resist underlayer film required in the semiconductor device substrate or the patterning step, for example, an aqueous hydrogen peroxide-containing ammonia solution called SC1 commonly used in semiconductor manufacturing processes. It becomes a composition for organic film formation which can form the organic film which can be easily wet-removed with the silicon powder residue modified | denatured by the etching. Moreover, if it is such a composition for organic film formation, it becomes possible to apply as a material for ion implantation masks at the time of forming a three-dimensional transistor.

At this time, it is preferable that 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 fruit water and directly above an organic resist underlayer film poorly soluble in ammonia fruit water.

The composition for forming an organic film of the present invention is an organic film (hereinafter also referred to as the present organic film) formed between an organic resist underlayer film and a silicon-containing resist intermediate film formed directly under a photoresist in a three-layer resist method formed on a substrate. ) Can be formed (hereinafter also referred to as the present composition), and is an organic film-forming composition capable of forming a real four-layer resist. An organic resist underlayer film is formed on the substrate, the organic film is formed between the organic resist underlayer film and the silicon-containing resist interlayer, and then a silicon-containing resist interlayer is formed, and further an upper resist is formed, followed by a pattern with an upper resist. The pattern can be transferred to the silicon-containing resist intermediate film by dry etching, and the organic film and the organic resist underlayer film are dry-etched at a time by using the transferred pattern as a mask to transfer the pattern. Here, if the silicon-containing resist intermediate film is soluble in ammonia fruit water and the organic resist underlayer film is poorly soluble in ammonia fruit water, the silicon content remaining on the transferred pattern as described above can be removed with the ammonia fruit water together with the present organic film. As a result, an organic resist underlayer film pattern having no silicon powder residue can be obtained. Applying this organic resist underlayer film pattern as an ion implantation shielding mask enables accurate ion implantation even in a three-dimensional transistor with a large step difference, thereby enabling three-dimensional transistor processing with high yield.

At this time, it is preferable that the silicon-containing resist interlayer contains one or both of boron and phosphorus.

When the pattern-formed silicon-containing resist intermediate film is used as a mask and the pattern is transferred to the organic film and the organic resist underlayer film by dry etching at once, the silicon-containing resist intermediate film pattern undergoes structural changes due to the action of gas or plasma during dry etching. The solubility to ammonia and water may fall. However, since the silicon-containing resist intermediate film contains either or both of boron and phosphorus, the silicon-containing resist intermediate film and / or the silicon powder residue which are soluble in ammonia fruit water can be made even after dry etching regardless of the dry etching gas or conditions. have.

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

If the composition for forming an organic film of the present invention contains either or both of a thermal acid generator and a crosslinking agent, the organic film having a uniform composition can be formed on the organic resist underlayer film with a uniform film thickness, and the organic It is possible to suppress the occurrence of intermixing when forming a silicon-containing resist intermediate film on the film.

At this time, the composition for forming an organic film was spin-coated on a substrate and subsequently heated, thereby treating with a solution at 65 ° C. mixed with 29% aqueous ammonia / 35% hydrogen peroxide / water = 1/1/8. By, it is desirable to provide an organic film having a dissolution rate of 5 nm / min or more.

If it is the composition for organic film formation which provides the organic film which has such a performance, the organic film and the silicon powder residue on this organic film can be fully removed with ammonia fruit water, without damaging the board | substrate for semiconductor device manufacture.

Furthermore, it is preferable that the said composition for organic film formation provides the organic film whose film thickness is 10 nm or more and less than 100 nm.

If the composition for forming an organic film that provides an organic film having such a film thickness is used, the accuracy of the pattern formed of the upper layer resist can be maintained even if the pattern is transferred to the organic film and the organic resist underlayer film at a time by using the silicon-containing resist intermediate film as a dry etching mask. The pattern can be transferred in the held state.

If such an organic film-forming composition is modified by dry etching using a stripping solution which does not damage the organic resist underlayer film required in the semiconductor device substrate or the patterning process, for example, ammonia fruit water called SC1 generally used in the semiconductor manufacturing process. It becomes the composition for organic film formation which can form the organic film which can be easily wet-removed with the silicon powder residue which became. Further, by applying the composition for forming an organic film of the present invention between an organic resist underlayer film and a silicon-containing resist intermediate film, it is possible to form an ion implantation mask in which silicon powder does not remain on the pattern during formation of the shielding mask for ion implantation. Done. As a result, a decrease in yield in the manufacturing process of the three-dimensional transistor can be prevented, and a higher performance semiconductor device can be economically manufactured.

As described above, a silicon powder modified by dry etching using a stripping solution that does not damage an organic resist underlayer film required in a semiconductor device substrate or a patterning process, for example, ammonia fruit water called SC1 which is generally used in a semiconductor manufacturing process. There is a demand for a composition for forming an organic film that can form an organic film that can be easily wet-removed with the residue.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the said subject, this inventor contains the high molecular compound and organic solvent which have any 1 or more types of repeating units represented by following General formula (1)-(4), and the said organic solvent In the present invention, the present invention is completed by finding out that the above problem can be solved if the composition for forming an organic film in which at least one total selected from propylene glycol esters, ketones, and lactones comprises more than 30 wt% of the total organic solvent. I was.

That is, this invention is a composition for organic film formation, The composition for organic film formation contains the high molecular compound and organic solvent which have any 1 or more types of repeating units represented by following General formula (1)-(4). In the organic solvent, at least one total selected from propylene glycol esters, ketones, and lactones is an organic film-forming composition that accounts for more than 30 wt% of the total organic solvent.

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

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to these.

[Organic Film Formation Composition]

The composition for organic film formation of this invention contains a high molecular compound and an organic solvent. Hereinafter, each component is further explained in full detail.

<Polymer compound>

The high molecular compound in the composition for organic film formation of this invention has any 1 or more types of repeating units represented by following General formula (1)-(4).

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

Here, what has the following structures can be illustrated as a repeating unit represented by General formula (1).

As a repeating unit represented by General formula (2), the thing of the following structures can be illustrated.

As a repeating unit represented by General formula (3), the thing of the following structures can be illustrated.

As a repeating unit represented by General formula (4), what has the following structure can be illustrated.

Among these, what is represented by the said General formula (2) or (3) can be illustrated as a preferable repeating unit. If the composition for forming an organic film containing a high molecular compound having such a repeating unit, the highly polar carboxyl group is effectively located, it is possible to form an organic film excellent in wet removal by ammonia and water.

Here, as a repeating unit represented by the said General Formula (1)-(4), As a monomer for obtaining what is n = 0, Phenol, o-cresol, m-cresol, p-cresol, 2, 3- dimethyl phenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5- Trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, cate Kohl, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4 Isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, 4-phenylphenol, tritylphenol, pyrogallol, thymol, hydroxyphenylglycidyl ether, 4- Fluorophenol, 3,4-difluorophenol, 4-trifluoromethylphenol, 4-chlorophenol, 4-hydroxybenzenesulfonic acid, 4-vinylphenol, 1- (4- 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, 7-methoxy-2-naphthol, and 1,2-dihydrate Loxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 5-amino-1-naphthol, 2-methoxycarbonyl-1 -Naphthol, 6- (4-hydroxyphenyl) -2-naphthol, 6- (cyclohexyl) -2-naphthol, 1,1'-B2,2'-naphthol, 6,6'-B2,2'- Naphthol, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 6-hydroxy-2-vinylnaphthalene, 1-hydroxymethylnaphthalene, 2-hydroxymethylnaphthalene, 8-hydroxynaphthalene -1-sulfonic acid, 2-hydroxynaphthalene-7-sulfonic acid, 2,3-dihydroxynaphthalene-7-sulfonic acid, 1,7-dihydroxynaphthalene-3-sulfonic acid, and the like. .

These may be used independently, respectively and may combine two or more types in order to control n value, k value, and etching tolerance.

The following aldehyde compounds can be illustrated as a condensation agent to make condensation reaction with these monomers. For example, formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, cyclopentanecarboxyaldehyde, cyclopentenecarboxyaldehyde, cyclohexanecarboxyaldehyde, cyclohexene carboxyaldehyde, norbornanecarboxaldehyde, norbornene carboxaldehyde Aldehyde, adamantanecarboaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-di Hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitro Benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbene Zaldehyde, 2-ethylbenzaldehyde, 3-ethylbenzaldehyde, 4-ethylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, anthracenecarboaldehyde, pyrenecarboaldehyde, furfural, etc. Can be mentioned.

In addition, the compound which can be represented by the following formula can be illustrated.

The ratio of the monomer and the aldehyde compound that is the condensing agent is preferably 0.01 to 5 mol, more preferably 0.05 to 2 mol, with respect to 1 mol of the total amount of the molar amount of the monomer.

As a ratio in all the repeating units which the repeating unit represented by the said General Formula (1)-(4) occupies, the whole is made into 100%, 10% or more is preferable, More preferably, it is 30% or more.

When the polycondensation reaction is carried out using the raw materials as described above, the acid or base is usually used as a catalyst in a solvent or a solvent, and can be carried out at room temperature or under cooling or heating, if necessary, and thus a high molecular compound (polymer). Can be obtained. Examples of the solvent 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 trichloroethylene Chlorine solvents, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, nitriles such as acetonitrile, ketones such as acetone, ethyl methyl ketone and isobutyl methyl ketone, ethyl acetate, n-butyl acetate, Esters such as propylene glycol methyl ether acetate, lactones such as γ-butyrolactone, dimethyl sulfoxide, N, N-dimethylformamide, and hexamethylforce Aprotic polar solvents, such as polytriamide, can be illustrated and these can be used individually or in mixture of 2 or more types. These solvents can be used in the range of 0-2,000 mass parts with respect to 100 mass parts of reaction raw materials.

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, and trichloride. Aluminum, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyl dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride Lewis acids, such as titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxy and titanium (IV) 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, methyl lithium, n-butyllithium, methyl magnesium chloride, Alkyl metals such as ethyl magnesium bromide, alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide, triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4-dimethylamino Organic bases, such as a pyridine, can be used. The amount of use is preferably 0.001 to 100% by weight, more preferably 0.005 to 50% by weight with respect to the raw material. As for reaction temperature, the boiling point degree of a solvent is preferable from -50 degreeC, and 100 degreeC is more preferable from room temperature.

As a method of a polycondensation reaction, the method of putting a monomer, a condensing agent, and a catalyst collectively, and the method of dripping a monomer and a condensing agent in the presence of a catalyst are mentioned.

Moreover, in order to remove the unreacted raw material, a catalyst, etc. which exist in a system after completion | finish of a polycondensation reaction, the temperature of a reaction pot is raised to 130-230 degreeC, and the method of removing volatile matters about 1-50 mmHg, and a suitable solvent The method of fractionating a polymer by adding water, the method of dissolving the polymer in a good solvent and then reprecipitating in a poor solvent can be used according to the properties of the obtained reaction product.

As molecular weight of polystyrene conversion of the polymer obtained in this way, it is preferable that weight average molecular weights (Mw) are 500-500,000, and it is especially preferable that it is 1,000-100,000. In addition, the dispersion degree of molecular weight uses the inside of the range of 1.2-20 suitably. By cutting the monomer component, oligomer component or low molecular weight (Mw) of 1,000 or less, the volatile components in the bake can be suppressed to prevent surface defects caused by contamination around the bake cup or the deposited volatile components falling on the wafer. .

<Organic solvent>

The composition for organic film formation of this invention contains an organic solvent. Specific examples of the organic solvent include ketones such as cyclopentanone, cyclohexanone, and methyl-2-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1 Alcohols such as ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, 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, tert-butyl propionate, propylene glycol Esters such as monotert-butyl ether acetate, and γ-butyrolactone, and the like, and one or two or more thereof may be used in combination. Although it is possible, it is not limited to these.

Here, in the organic solvent, at least one selected from propylene glycol ester, ketone, and lactone (for example, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, methyl-2-amyl in the above-described organic solvents). The total of one or more selected from ketones and γ-butyrolactones) must account for more than 30 wt% of the total organic solvent. If the organic solvent does not satisfy this condition, a homogeneous organic film cannot be formed directly on the organic resist underlayer film.

Moreover, the acid generator and crosslinking agent for further promoting a crosslinking reaction can be added to the composition for organic film formation of this invention. As an acid generator, although an acid is generated by thermal decomposition (thermal acid generator) and an acid is generated by irradiation of light, either can be added.

Examples of the acid generator include onium salts, diazomethane derivatives, glyoxime derivatives, bis sulfone derivatives, sulfonic acid esters of N-hydroxyimide compounds, β-ketosulfonic acid derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonates, Sulfonic acid ester derivatives; Specific examples include those described in paragraphs (0081) to (0111) of JP 2008-65303 A (US Patent Application Publication No. 2008/0038662 (A1) specification).

Examples of the crosslinking agent include melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and eggs substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. The compound containing double bonds, such as a kenyl ether group, etc. are mentioned. Specifically, what was described in Paragraph (0074)-(0080) of Unexamined-Japanese-Patent No. 2008-65303 (the specification of US patent application publication 2008/0038662 (A1)) is mentioned.

Moreover, surfactant can also be added to the composition for organic film formation of this invention in order to improve the applicability | paintability in spin coating. As surfactant, Nonionic surfactant of polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Fluorine-based surfactants, partially fluorinated oxetane ring-opening polymer-based surfactants, and the like. Specific examples include those described in paragraphs (0142) to (0147) of JP2009-269953A (US Patent Application Publication No. 2009/0274978 (A1) specification).

Moreover, the basic compound for improving storage stability can be added to the composition for organic film formation of this invention. The basic compound serves as a quencher for the acid to prevent the acid generated in a smaller amount than the acid generator from advancing the crosslinking reaction. As such a basic compound, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group And a compound, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like. Specific examples include those described in paragraphs (0112) to (0119) of JP 2008-65303 A (US Patent Application Publication No. 2008/0038662 (A1)).

The composition for forming an organic film of the present invention as described above can be suitably used for formation of an organic film to be introduced immediately below a silicon-containing resist intermediate film soluble in ammonia fruit water and directly above an organic resist underlayer film poorly soluble in ammonia fruit water.

Moreover, it is preferable that the composition for organic film formation of this invention provides the organic film whose film thickness is 10 nm or more and less than 100 nm, It is more preferable that film thickness is 20 nm or more and 80 nm or less. If the thickness of the organic film is 10 nm or more, the effect of removing the silicon powder by wet treatment can be sufficiently obtained. If the thickness of the organic film is less than 100 nm, the side etching during the dry etching process can be suppressed, so that there is no fear of problems in processing. do.

[Organic membrane]

By the composition for organic film formation of this invention, an organic film can be formed. As a method of forming an organic film using the composition for organic film formation of this invention, the method of coating the above-mentioned composition for organic film formation of this invention on a to-be-processed substrate by a spin coat method etc. is mentioned. After spin coating, the solvent is evaporated to bake in order to accelerate the crosslinking reaction in order to prevent mixing with the resist upper layer film or the resist intermediate layer film. Baking is performed within 100 to 400 degreeC, and is 10 to 600 second, Preferably it is within the range of 10 to 300 second. Baking temperature becomes like this. More preferably, they are 150 degreeC or more and 350 degrees C or less.

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

As such a silicon-containing resist intermediate film, it is preferable to be soluble in ammonia fruit water and to be able to dissolve or peel off with ammonia fruit water. For example, Japanese Patent Application Laid-Open No. 2010-085912 (US Patent Application Publication No. 2010/0086870 (A1) specification), Japanese Patent Publication No. 2010-085893 (US Patent Application Publication No. 2010/0086872 (A1) specification), Japanese Patent Application Laid-Open No. 2015-028145 (US Patent Application Publication No. 2015/0004791 (A1) specification), International Publication No. 2010/068336 (US Patent Application Publication No. 2011/0233489 (A1) specification), Japanese Patent Publication Silicon-containing resist underlayer as described in 2016-074772 (US Patent Application Publication No. 2016/0096977 (A1) specification) and Japanese Patent Publication No. 2016-074774 (US Patent Application Publication No. 2016/0096978 (A1) specification) It is preferable to use the film as the silicon-containing resist intermediate film in the present invention. Among these, containing either or both of boron and phosphorus is particularly preferable because it is excellent in wet removal by ammonia and water.

Moreover, as an organic resist underlayer film which can be applied by this invention, what is resistant to ammonia fruit water (that is, it is poorly soluble in ammonia fruit water) is preferable. For example, Japanese Patent Application Laid-Open No. 2004-205685 (US Patent No. 7,427,464 (B2) Specification), Japanese Patent Publication No. 2010-122656 (US Patent Application Publication No. 2010/0099044 (A1) and US Patent Application Publication No. 2013 / 0184404 (A1) specification, Japanese Patent Application Laid-Open No. 2012-214720 (US Patent Application Publication No. 2012/0252218 (A1) Specification), Japanese Patent Application Laid-Open No. 2016-094612 (US Patent Application Publication No. 2013/0337649) The organic resist underlayer film disclosed by (A1) specification) can be used.

The organic resist underlayer film is formed by coating the organic resist underlayer film composition on the substrate to be processed by a spin coating method or the like. By using the spin coating method or the like, good embedding characteristics can be obtained. After spin coating, the solvent is evaporated to bake to promote crosslinking reaction in order to prevent mixing with the resist upper layer film or the resist intermediate film. Baking is performed within 100 to 600 degreeC, and is 10 to 600 second, Preferably it is within the range of 10 to 300 second. Baking temperature becomes like this. More preferably, they are 200 degreeC or more and 500 degrees 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 ° C. or lower, more preferably 500 ° C. or lower.

In the method for forming the organic resist underlayer film as described above, 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 an atmosphere such as air, N ₂ , Ar, He, or the like. By hardening, it can form an organic resist underlayer film. By baking this organic resist underlayer film composition in the atmosphere containing oxygen, the cured film resistant to ammonia fruit water can be obtained.

By forming the organic resist underlayer film in this way, a flat cured film can be obtained regardless of the irregularities of the substrate to be processed by the excellent embedding / flattening properties, so that a flat cured film is formed on a substrate having a height of 30 nm or more or a step. Very useful when forming.

Moreover, although the thickness of this organic resist underlayer film for semiconductor device manufacture and flattening is selected suitably, it is preferable to set it as 5-500 nm, especially 10-400 nm.

When the composition for forming an organic film of the present invention is applied to the formation of an organic film to be introduced immediately below a silicon-containing resist intermediate film and directly above an organic resist underlayer film, and the shielding mask for ion implantation is formed, the above-described organic film and silicon In order to wet-remove the containing resist intermediate film, the peeling liquid containing hydrogen peroxide is preferable. At this time, in order to promote peeling, it is more preferable to adjust pH by adding acid or alkali to the stripping solution. Examples of such pH regulators (acids or alkalis) 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, alkalis containing nitrogen such as ammonia, ethanolamine and tetramethylammonium hydroxide, and EDTA Organic acid compounds containing nitrogen, such as diamine tetraacetic acid), etc. can be illustrated. Especially ammonia is preferable. That is, as said peeling liquid, ammonia and water are preferable.

When ammonia and water are used as the stripping solution, the ratio of ammonia, hydrogen peroxide, and deionized water for dilution is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and more preferably 100 parts by mass of deionized water. It is 0.1-10 mass parts, and hydrogen peroxide is 0.01-20 mass parts, Preferably it is 0.05-15 mass parts, More preferably, it is 0.1-10 mass parts.

Wet removal only needs to prepare the peeling liquid of 0 degreeC-80 degreeC, Preferably 5 degreeC-70 degreeC, and to immerse the silicon wafer in which the to-be-processed substrate to be processed is formed. If necessary, the organic film formed by the silicon-containing resist intermediate film and the organic film-forming composition of the present invention can be easily removed in accordance with the procedures of the method, such as spraying the stripping solution on the surface or applying the stripping solution while rotating the wafer. have.

In particular, the composition for forming an organic film of the present invention is treated with a solution at 65 ° C. mixed with 29% aqueous ammonia / 35% hydrogen peroxide / water = 1/1/8 by spin coating on a substrate and subsequently heating. By, it is desirable to provide an organic film having a dissolution rate of 5 nm / min or more.

Moreover, it is preferable to confirm the removal degree of a silicon powder by quantifying the silicon | silicone which remain | survives on the surface of an organic resist underlayer film after ammonia perwater treatment. For example, it can analyze by the method of Unexamined-Japanese-Patent No. 2016-177262 (The specification of US patent application publication 2016/0276152 (A1)).

As described above, in the organic film-forming composition of the present invention, a peeling liquid that does not damage the organic resist underlayer film required in the semiconductor device substrate or the patterning process, for example, ammonia fruit tree called SC1 which is generally used in the semiconductor manufacturing process It becomes the composition for organic film formation which can form the organic film which can be easily wet-removed with the silicon powder residue modified | denatured by dry etching. Further, by applying the composition for forming an organic film of the present invention between an organic resist underlayer film and a silicon-containing resist intermediate film, it is possible to form an ion implantation mask in which silicon powder does not remain on the pattern during formation of the shielding mask for ion implantation. Done. As a result, it is possible to prevent a decrease 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, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description. In addition, in the following example,% showed the mass% and molecular weight measurement was performed by GPC. In GPC measurement, detection was performed by RI, the eluting solvent was made into tetrahydrofuran, and the molecular weight of polystyrene conversion was calculated | required.

Synthesis of Polymer Compound

Synthesis Example (A1)

To a 500 ml three-necked flask, 40.00 g (0.36 mol) of resorcinol, 10.00 g of a 20% by mass PGME solution of p-toluenesulfonic acid monohydrate and 72.00 g of 2-methoxy-1-propanol were taken and stirred to 80 ° C. Heated. 23.59 g (0.29 mol of formaldehyde) 37% formalin was added there, and it stirred for 11 hours. 160 g of ultrapure water and 200 g of ethyl acetate were added to the reaction solution, which was transferred to a separatory funnel, and washed with 150 g of ultrapure water in order to remove the acid catalyst and metal impurities. The obtained organic layer was concentrated under reduced pressure to 76 g, ethyl acetate was added to obtain a 150 g solution, and 217 g of n-hexane was added. The n-hexane layer was separated into an upper layer and the high concentration polymer solution became a 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 ° C. for 13 hours to obtain a polymer compound A1. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw = 800 and Mw / Mn = 1.3. This high molecular compound A1 has a repeating unit represented by General formula (4).

Synthesis Example (A2)

In a 1,000 ml three-necked flask, 80.1 g (0.50 mol) of 1,5-dihydroxynaphthalene, 26.4 g (0.24 mol) of 37% formalin solution and 250 g of 2-methoxy-1-propanol were dissolved under nitrogen atmosphere at 80 ° C. 18 g of 20% paratoluenesulfonic acid 2-methoxy-1-propanol solution was slowly added to the solution, and stirred at a liquid temperature of 110 ° C for 12 hours. 500 g of methyl isobutyl ketones were added after cooling to room temperature, and the organic layer was wash | cleaned 5 times with 200 g of pure waters, 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 a polymer compound A2. When weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, it was Mw = 3,000 and Mw / Mn = 2.7. This high molecular compound A2 has a repeating unit represented by General formula (4).

Synthesis Example (A3)

In a 2,000 ml three-necked flask, 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-1-propanol The mixture was made into a homogeneous solution at a liquid temperature of 80 ° C. under a nitrogen atmosphere, and then 6.4 g of a 25% sodium hydroxide aqueous solution was slowly added thereto, followed by stirring at a liquid temperature of 110 ° C. for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A3. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 2,900 and Mw / Mn was 2.9. This high molecular compound A3 has a repeating unit represented by General formula (1).

Synthesis Example (A4)

To a 1,000 mL flask, 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, and p-toluenesulfonic acid was stirred at 70 ° C. 20 g of 20% by mass methylcellosolve solution was added. The temperature was raised to 85 ° C, stirred for 6 hours, cooled to room temperature, and diluted with 800 mL of ethyl acetate. The mixture was transferred to a separating funnel, and the washing was repeated with 200 mL of deionized water to remove the reaction catalyst and metal impurities. The resulting 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 collected by filtration, recovered, and dried under reduced pressure to obtain a polymer compound A4. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 3,800 and Mw / Mn was 2.4. This high molecular compound A4 has a repeating unit represented by General formula (1).

Synthesis Example (A5)

In a 2,000 ml three-necked flask, 80.1 g (0.50 mol) of 2,7-dihydroxynaphthalene, 100.1 g (0.40 mol) of terephthalaldehyde acid = t-butyl and 600 g of 2-methoxy-1-propanol under nitrogen atmosphere After making it a homogeneous solution at 80 degreeC of liquid temperature, 6.4g of 25% sodium hydroxide aqueous solution was added slowly, and it stirred at liquid temperature of 110 degreeC for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A5. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 2,900 and Mw / Mn was 2.9. This high molecular compound A5 has a repeating unit represented by General formula (2).

Synthesis Example (A6)

In a 2,000 ml three-necked flask, 94.4 g (0.50 mol) of 6-hydroxy-2-naphthoic acid, 100.1 g (0.40 mol) of terephthalaldehyde acid = t-butyl and 600 g of 2-methoxy-1-propanol were nitrogen atmosphere. After making it into a homogeneous solution at 80 degreeC under liquid solution, 6.4g of 25% sodium hydroxide aqueous solution was added slowly, and it stirred at liquid temperature of 110 degreeC for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A6. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 3,500 and Mw / Mn was 2.8. This high molecular compound A6 has a repeating unit represented by General formula (2).

Synthesis Example (A7)

In a 2,000 ml three-necked flask, 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 added under a nitrogen atmosphere at 80 ° C. After making it into a homogeneous solution, 6.4 g of 25% sodium hydroxide aqueous solution was slowly added, and it stirred at liquid temperature 110 degreeC for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A7. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 2,200 and Mw / Mn was 2.9. This high molecular compound A7 has a repeating unit represented by General formula (2).

Synthesis Example (A8)

In a 200 ml three-necked flask, 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 under a nitrogen atmosphere were heated at 80 ° C. 0.6 g of 25% aqueous sodium hydroxide solution was slowly added thereto, followed by stirring at a liquid temperature of 110 ° C. for 24 hours. After cooling to room temperature, 150 g of ethyl acetate was added, the organic layer was washed with 30 g of a 3% nitric acid aqueous solution, and further washed with 30 g of pure water five times, 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 a polymer compound A8. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw = 2,000 and Mw / Mn = 2.6. This high molecular compound A8 has a repeating unit represented by General formula (2).

Synthesis Example (A9)

In 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-1-propanol The mixture was made into a homogeneous solution at a liquid temperature of 80 ° C. under a nitrogen atmosphere, and then 6.4 g of a 25% sodium hydroxide aqueous solution was slowly added thereto, followed by stirring at a liquid temperature of 110 ° C. for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A9. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 3,200 and Mw / Mn was 3.0. This high molecular compound A9 has a repeating unit represented by General formula (3).

Synthesis Example (A10)

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-1-propanol in a 2,000 ml three-necked flask The mixture was made into a homogeneous solution at a liquid temperature of 80 ° C. under a nitrogen atmosphere, and then 6.4 g of a 25% sodium hydroxide aqueous solution was slowly added thereto, followed by stirring at a liquid temperature of 110 ° C. for 24 hours. After cooling to room temperature, 1,500 g of ethyl acetate was added, the organic layer was washed with 300 g of a 3% nitric acid aqueous solution, and further washed with 300 g of pure water five times, and dried 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 a polymer compound A10. The weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were calculated | required by GPC, and Mw was 2,700 and Mw / Mn was 2.7. This high molecular compound A10 has a repeating unit represented by General formula (3).

[Examples and Comparative Examples]

The organic solvent containing the above-mentioned high molecular compound A1-A10, crosslinking agent XL1-3 as an additive, thermal-acid generator AG1, and 0.1 mass% of FC-4430 (made by Sumitomo 3M Co., Ltd.) as surfactant is mixed by the ratio shown in Table 1. And the composition for organic film formation (Sol.1-19) was prepared, respectively, by filtering with a 0.1 micrometer fluorine resin filter. Where Sol. 1-10, 17-19 are the composition for organic film formation of this invention, Sol. 11-16 are compositions for organic film formation for comparison. In addition, in the prepared composition for organic film formation, the quantity which the 1 or more types of sum total chosen from a propylene glycol ester, a ketone, and a lactone occupies all the organic solvents is combined with Table 1, and is shown.

The thermal acid generator AG1 and the crosslinking agents XL1 to 3 are shown below.

In addition, in Table 1, an organic solvent means the following.

PGMEA: propylene glycol methyl ether acetate

Cyho: cyclohexanone

PGEE: propylene glycol ethyl ether

GBL: γ-butyrolactone

4M2P: 4-methyl-2-pentanol

[Solvent Resistance Evaluation: Examples 1-1 to 13, Comparative Examples 1-1 to 6]

Since the silicon-containing resist intermediate film is spin-coated immediately above the organic film formed by the composition for organic film formation of this invention, resistance to the organic solvent was evaluated in order to investigate whether the organic film formed is an organic film which does not produce intermixing. . The above-mentioned composition for forming an organic film (Sol. 1 to 19) was each applied onto a silicon substrate, baked at 285 ° C. for 60 seconds to form an organic film, and the film thickness T1 was measured. After spin coating PGMEA / PGME = 30/70 (mass ratio) on the obtained organic film, it heat-processed at 100 degreeC for 30 second, and measured the film thickness T2. From these measurement results, the film thickness reduction 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. Organic films formed of 1 to 10 and 17 to 19 have sufficient organic solvent resistance. Therefore, even if the silicon-containing resist intermediate film is spin-coated directly on these organic films, it became clear that a laminated film can be formed without intermixing.

[Evaluation of Film Formability on Organic Resist Underlayer Film: Examples 2-1 to 13, Comparative Examples 2-1 to 6]

Since the organic film formed by the composition for organic film formation of this invention is laminated | stacked on the organic resist underlayer film, the film formability on the organic resist underlayer film was confirmed. Shin-Etsu Chemical Co., Ltd. spin-on carbon film ODL-102 was apply | coated on a silicon wafer as an organic resist underlayer film, and the organic resist underlayer film with a film thickness of 200 nm was formed. The organic film formation composition (Sol.1-19) was apply | coated on this, it baked at 285 degreeC for 60 second, the organic film was formed, and the film-forming 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. 1-10 and 17-19 were able to form a film on the organic resist underlayer film without a film-forming defect by spin coating. On the other hand, as shown in Comparative Examples 2-1 to 6, Sol containing 70 wt% or more of an alcohol-based organic solvent. 11-16 could not be laminated | stacked because a splash occurred on the organic resist underlayer film.

[Wet removeability of organic membranes with ammonia and water: Examples 3-1 to 10]

The above-mentioned composition for forming an organic film (Sol. 1 to 10) was applied onto a silicon substrate, respectively, and baked at 285 ° C. for 60 seconds to form an organic film to be 25 nm, and the film thickness T1 was measured. The membrane was mixed with 29% ammonia water / 35% hydrogen peroxide water / water = 1/1/8 and soaked in ammonia fruit water maintained at 65 ° C. for 5 minutes, washed with pure water, and dried by heating at 100 ° C. for 60 seconds to obtain a film thickness. T3 was measured. Moreover, the film removal rate at this time was calculated | required. These results are shown in Table 4.

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

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

The spin-on carbon film ODL-102 manufactured by Shin-Etsu Chemical Co., Ltd. was formed on the silicon wafer as a film thickness of 200 nm as an organic resist underlayer film. The composition for organic film formation (Sol. 1-10, 17-19) of this invention was apply | coated on it, respectively, and it heated at 285 degreeC for 60 second, and laminated | stacked the organic film. On the other hand, in Comparative Example 4-1, no organic film was introduced.

Subsequently, the silicon-containing resist intermediate film formation composition (SiARC-1) shown in following Table 5 was apply | coated, it heated at 220 degreeC for 60 second, and the silicon-containing resist intermediate film with a film thickness of 35 nm was laminated | stacked. The positive development ArF resist solution (PR-1) shown in following Table 6 was apply | coated on it, and it heated at 110 degreeC for 60 second, and formed the photoresist film with a film thickness of 100 nm. Furthermore, the liquid immersion protective film composition (TC-1) shown in following Table 7 was apply | coated on this photoresist film, and it heated at 90 degreeC for 60 second, and formed the protective film with a film thickness of 50 nm.

Subsequently, these wafers were exposed with an ArF immersion exposure apparatus (NSR-S610C manufactured by Nikon Corporation, NA 1.30, sigma 0.98 / 0.65, 35 degree dipole polarized light illumination, 6% halftone phase shift mask), and then exposed to 60 at 100 ° C. It baked for the first time (PEB), and developed for 30 second with 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, and obtained the positive line-and-space pattern of 160 nm1: 1. With respect to the wafer thus obtained, the cross-sectional shape of the pattern was observed with Hitachi Seisakusho electron microscope (S-4800), and the collapse of the pattern was observed with Hitachi High-Technologies electron microscope (CG4000). did.

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

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 / water = 1/1/8 and maintained at 65 ° C. with ammonia fruit water. 5 minutes treatment. After the treatment, the mixture was washed with pure water and dried by heating at 100 캜 for 60 seconds. In addition, in order to confirm that the silicon content could be removed by ammonia and water treatment, the surface of the organic resist underlayer film was analyzed by XPS with K-ALPHA manufactured by Thermo Fisher Scientific Co., Ltd. to quantify the silicon on the organic resist underlayer film. did.

The organic resist underlayer film pattern obtained by the above process was processed under the processing conditions shown in Table 10 using the Tokyo Electron etching apparatus Telius, and the residual organic resist underlayer film was ashed. The wafer after the ashing treatment was observed with an electron microscope (CG4000) manufactured by Hitachi Technologies Co., Ltd. to confirm the presence or absence of a residue. The results are shown in Table 11.

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

TPSNO ₃ : Triphenylsulfonium Nitrate

The molecular weight and 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-mentioned positive developing ArF resist solution (PR-1) is shown in Table 6 below.

The molecular weight, dispersion degree, and 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 (Mw / Mn) = 1.78

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

Base shown in Table 6: Structural formula of Quencher is shown below.

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

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

Protective Film Polymer: Molecular Weight (Mw) = 8,800

Dispersion (Mw / Mn) = 1.69

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

The dry etching processing conditions of the organic resist underlayer film are shown in Table 9 below.

Ashing conditions of the organic resist underlayer film are shown in Table 10 below.

As a result of observation of the cross-sectional shape of the photoresist pattern and pattern collapse obtained in the residue evaluation after the above-mentioned organic resist underlayer film ashing, the observation of the pattern cross-sectional shape after the dry etching process, the residual amount of silicon on the surface of the organic resist underlayer film after ammonia water treatment 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, Sol. Which can be removed with ammonia and water. When an organic film formed of 1 to 10 was introduced, silicon did not remain on the organic resist underlayer film after ammonia perwater treatment, and no residue occurred after ashing the organic resist underlayer film pattern. In addition, when the influence of the film thickness of the organic film was confirmed in Examples 4-11 to 13 and Comparative Example 4-1, when the organic film is thin, as shown in Example 4-11, the organic resist underlayer film after ammonia perwater treatment The silicon powder residue was not seen on the surface, and the residue did not occur after the ashing of the organic resist underlayer film pattern. In addition, as shown in Example 4-13, when a film was thick, although side etching entered into the organic film part at the time of a dry etching process, the residue did not generate | occur | produce after ashing the organic resist underlayer film pattern. On the other hand, as shown in Comparative Example 4-1, when there was no organic film, the removal effect of the silicon powder residue could not be obtained, and the residue occurred after ashing the organic resist underlayer film pattern.

As mentioned above, if it is the composition for organic film formation of this invention, it is easy to wet together with the silicon powder residue modified | denatured by dry etching using the peeling liquid which does not damage the organic resist underlayer film required by a semiconductor device board | substrate or a patterning process. It became clear that it became the composition for organic film formation which can form a removable organic film, and is applicable as a material for ion implantation shielding masks at the time of forming a three-dimensional transistor. In particular, it has become clear that by introducing the organic film in a film thickness of 10 nm or more and less than 100 nm, a processing process in which no residue occurs can be more reliably constructed. As a result, a decrease in yield in the manufacturing process of the three-dimensional transistor can be prevented, and a higher performance semiconductor device can be economically manufactured.

In addition, this invention is not limited to the said embodiment. The said embodiment is an illustration, Any thing which has a structure substantially the same as the technical idea described in the claim of this invention, and exhibits the same effect is included in the technical scope of this invention.

Claims (9)

As a composition for organic film formation,
The said organic film formation composition contains the high molecular compound and organic solvent which have any 1 or more types of repeating units represented by following General formula (1)-(4), In the said organic solvent, Propylene glycol ester and a ketone And at least one sum total selected from lactones comprises more than 30 wt% of the total organic solvent,
The composition for forming an organic film, 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 fruit water and directly above an organic resist underlayer film poorly soluble in ammonia fruit water. :

In formula, R <_1> is a C1-C19 hydrocarbon group, 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 which produces an acidic functional group by heating or the action of an acid. R <_3> is a C1-C16 hydrocarbon group which may have a hydrogen atom, a furanyl group, or a chlorine atom or a nitro group. k ₁ , k ₂ and k ₃ are 1-2, l is 1-3, m is 0-3 and n is 0 or 1. The composition for forming an organic film according to claim 1, wherein the silicon-containing resist intermediate film contains any one or both of boron and phosphorus. The composition for forming an organic film according to claim 1, wherein the composition for forming an organic film further contains any one or both of a thermal acid generator and a crosslinking agent. The composition for forming an organic film according to claim 2, wherein the composition for forming an organic film further contains any one or both of a thermal acid generator and a crosslinking agent. The composition for forming an organic film according to any one of claims 1 to 4, wherein the composition for forming an organic film is spin-coated on a substrate and subsequently heated to obtain 29% aqueous ammonia / 35% hydrogen peroxide / water = 1/1/8. A composition for forming an organic film, characterized by providing an organic film having a dissolution rate of 5 nm / min or more by treatment with a 65 ° C. solution mixed with a solution. The composition for forming an organic film according to any one of claims 1 to 4, wherein the composition for forming an organic film 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 5, wherein the composition for forming an organic film provides an organic film having a film thickness of 10 nm or more and less than 100 nm. delete delete