JP5170511B2 - Silicon-containing resist underlayer film forming composition for forming electron beam cured silicon-containing resist underlayer film - Google Patents

Description

  The present invention relates to a composition for forming a resist underlayer film between a semiconductor substrate and a photoresist. Specifically, the present invention relates to a resist underlayer film forming composition for forming, by electron beam irradiation, a resist underlayer film used as a lower layer of a photoresist in a lithography process for manufacturing a semiconductor device. The present invention also relates to a resist underlayer film forming method and a photoresist pattern forming method using the resist underlayer film forming composition.

  Conventionally, in the manufacture of semiconductor devices, fine processing by lithography using a photoresist has been performed. The microfabrication is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with an actinic ray such as ultraviolet ray through a mask pattern on which a semiconductor device pattern is drawn, and developing it. In this processing method, fine irregularities corresponding to the pattern are formed on the substrate surface by etching the substrate using the photoresist pattern as a protective film.

  In recent years, higher integration of semiconductor devices has progressed, and actinic rays used tend to be shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). Accordingly, the influence of diffuse reflection of active rays from the substrate and standing waves has become a serious problem. Therefore, in order to solve this problem, a method for providing an antireflection film between the photoresist and the substrate has been widely studied. As such an antireflection film, many studies have been made on an organic antireflection film because of its ease of use (see, for example, Patent Document 1).

  In recent years, in order to solve the problem of wiring delay that has become apparent as the pattern rules of semiconductor devices become finer, studies have been made on the use of copper as a wiring material. A dual damascene process has been studied as a wiring formation method. In the dual damascene process, a via hole is formed, and an antireflection film is formed on a substrate having a large aspect ratio. For this reason, antireflection films used in this process are required to have a filling characteristic that can fill holes without gaps, and a flattening characteristic that allows a flat film to be formed on the substrate surface. Yes. However, it is difficult to apply an organic antireflection film material to a substrate having a large aspect ratio, and in recent years, materials with emphasis on embedding characteristics and planarization characteristics have been developed (for example, , Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5.)

  In the manufacture of devices such as semiconductor devices, a barrier layer formed of a composition containing a crosslinkable polymer is interposed between the dielectric layer and the photoresist in order to reduce the poisoning effect of the photoresist by the dielectric layer. The method of providing is disclosed (for example, refer patent document 6).

  Thus, in the manufacture of semiconductor devices in recent years, in order to achieve various effects including an antireflection effect, a composition containing an organic compound is used between a semiconductor substrate and a photoresist, that is, as a lower layer of the photoresist. An organic resist underlayer film to be formed has been arranged.

By the way, these organic resist underlayer films are generally formed by applying a composition for forming a resist underlayer film on a semiconductor substrate and then heating the semiconductor substrate at a high temperature of about 170 ° C. to 200 ° C. Yes. Therefore, there has been a problem that the low molecular weight component contained in the resist underlayer film forming composition volatilizes or sublimates during heating at high temperature, adheres to the peripheral device, and contaminates the device. In addition, it has been a problem that a component adhering to the apparatus falls on the semiconductor substrate and adversely affects pattern formation.
US Pat. No. 5,919,599 JP 2000-294504 A JP 2002-47430 A JP 2002-190519 A International Publication No. 02/05035 Pamphlet JP 2002-128847 A

An object of the present invention is to provide a silicon atom-containing resist underlayer film forming composition for curing and forming a resist underlayer film used as a lower layer of a photoresist by electron beam irradiation in a lithography process for manufacturing a semiconductor device. is there. Another object of the present invention is to provide a method for forming a resist underlayer film used as a lower layer of a photoresist in a lithography process for manufacturing a semiconductor device using the composition, and a method for forming a photoresist pattern. By containing 5 to 45%, the plasma etching rate by oxygen gas is reduced, and a hard mask layer having etching resistance is obtained.
That is, since the resist pattern has a higher etching rate than the photoresist under the fluorine-based gas (for example, CF ₄ ) gas condition used when the resist underlayer film of the present invention is etched by the photoresist pattern, the formed resist film and the resist underlayer film The substrate can be processed using as a protective film.

In addition, since the etching rate is sufficiently higher than that of the photoresist under the fluorine-based gas (for example, CF ₄ ) gas condition used when the resist underlayer film of the present invention is etched by the photoresist pattern, the present invention is applied by the resist pattern. The resist underlayer film can be removed by etching, and the photoresist pattern can be transferred to the resist underlayer film of the present invention. Furthermore, when an organic film is formed under the present invention, it is far shorter than an organic film (having etching characteristics equivalent to those of a photoresist) under the O ₂ (oxygen) gas conditions used for etching the organic film. Therefore, the resist pattern transferred to the resist underlayer film (functioning as a hard mask) of the present invention can be further transferred to the organic film, and the semiconductor substrate is processed using the organic film as a protective film. can do.

  An object of the present invention is a resist underlayer film that does not cause intermixing with a photoresist applied and formed on an upper layer and has a higher dry etching rate in a fluorine gas system than a photoresist. It is providing the resist underlayer film forming composition for forming.

  Another object of the present invention is to provide a lower antireflection film for reducing reflection of exposure light from a substrate formed on a semiconductor substrate from a substrate in a lithography process for manufacturing a semiconductor device. A resist underlayer film forming composition for forming a resist underlayer film that can be used as a planarizing film for forming a resist and a film for preventing contamination of the photoresist by a substance generated from a semiconductor substrate during heating, etc. by light irradiation Is to provide.

  Another object of the present invention is to provide an inorganic antireflection film-forming composition containing a light absorbing compound for suppressing reflection / scattering from a semiconductor substrate.

As a first aspect, the present invention is a composition for forming a resist underlayer film used as a lower layer of a photoresist in a lithography process for manufacturing a semiconductor device by electron beam irradiation, and contains 5-45% by mass of silicon atoms. A resist underlayer film forming composition comprising a polymerizable compound (A) and a solvent (B),
As a second aspect, the resist underlayer film forming composition according to the first aspect, wherein the polymerizable substance is a compound having at least one reactive group capable of being polymerized by electron beam irradiation,
The resist underlayer film according to the second aspect, wherein the reactive group polymerizable by electron beam irradiation is a reactive group having an unsaturated multiple bond of carbon or carbon, or a reactive group having an epoxy group. Forming composition,
As a fourth aspect, the resist underlayer film forming composition according to the third aspect, wherein the reactive group having an unsaturated multiple bond of carbon and carbon is an acrylate group, a methacrylate group, or a vinyl ether group,
As a fifth aspect, the resist underlayer film forming composition according to the first aspect, wherein the polymerizable substance is a compound having 1 to 4 acrylate groups, methacrylate groups, or vinyl ether groups in the molecule,
As a sixth aspect, the polymerizable compound (A) containing a silicon atom is represented by the formula (I):
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (I)
(However, R ¹ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ³ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and R ² is a halogen atom or a carbon number of 1 to 8 is an alkoxy group, an alkoxyalkyl group, or an alkoxyacyl group, a is an integer of 1, b is an integer of 0, 1 or 2, and a + b is an integer of 1, 2 or 3.) and Formula (II):
[(R ⁴ ) _c Si (R ⁵ ) _3-c ] ₂ Y (II)
(However, R ⁴ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ⁵ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and Y is an oxygen atom, a methylene group, or a carbon number of 2 Represents an alkylene group of ˜20, and c is an integer of 1 or 2.) At least one silicon atom selected from the group consisting of an organosilicon compound represented by the following formula, a hydrolyzate thereof, and a condensate thereof: The resist underlayer film forming composition according to any one of the first to fifth aspects, which is a polymerizable compound (A1) to be contained,
As a seventh aspect, the polymerizable compound (A) containing the silicon atom is selected from the group consisting of the organosilicon compounds represented by the above formulas (I) and (II), hydrolysates thereof, and condensates thereof. A polymerizable compound (A1) containing at least one selected silicon atom;
Formula (III),
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (III)
(However, R ¹ and R ³ are each an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group having a mercapto group, an amino group, or a cyano group, and a silicon atom by a Si—C bond. R ² is a halogen atom, or an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an alkoxyacyl group, and a and b are each an integer of 0, 1, or 2. A + b is an integer of 0, 1, or 2) and formula (IV),
[(R ⁴ ) _c Si (X) _3−c ] ₂ Y (IV)
(However, R ⁴ represents an alkyl group having 1 to 5 carbon atoms, X represents an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkyl group or an alkoxyacyl group, and Y represents a methylene group or an alkylene having 2 to 20 carbon atoms. And c is an integer of 0 or 1. Polymerization containing at least one silicon atom selected from the group consisting of an organosilicon compound represented by: a hydrolyzate thereof, and a condensate thereof. The resist underlayer film forming composition according to any one of the first to fifth aspects, which is a combination with the compound (A2),
As an eighth aspect, the polymerizable compound (A) containing the silicon atom comprises the above (A1) or a combination of the above (A1) and (A2), and (A1) :( A2) is 100 in molar ratio. : Hydrolysis of an organosilicon compound of 0 to 50 and condensation thereof, which is a condensate having a polymerizable organic group having a weight average molecular weight of 100 to 100,000, according to any one of the first to fifth aspects. Resist underlayer film forming composition,
As a ninth aspect, the polymerizable compound (A) containing the silicon atom is an organosilicon compound comprising the above formula (I) or a combination of the above formula (I) and the formula (III), and the value of a + b is 1st viewpoint thru | or the condensate which has the polymerizable organic group of the weight average molecular weight 100-1 million which hydrolyzed the organosilicon compound which the organosilicon compound used as 1 contains in the ratio of 5-75 mass%, and condensed it The resist underlayer film forming composition according to any one of the fifth aspects,
As a tenth aspect, a step of forming a resist underlayer film by applying the resist underlayer film forming composition according to any one of the first to ninth aspects on a semiconductor substrate, and an electron beam on the resist underlayer film A method of manufacturing a semiconductor device including a step of curing the resist underlayer film by irradiation,
As an eleventh aspect, a step of applying the resist underlayer film forming composition according to any one of the first to ninth aspects on a semiconductor substrate to form a resist underlayer film, and an electron beam on the resist underlayer film A step of curing the resist underlayer film by irradiation, a step of forming a photoresist layer by applying and heating a photoresist composition on the resist underlayer film, and a coating with the resist underlayer film and the photoresist layer A semiconductor device including a step of exposing a semiconductor substrate, a step of developing a photoresist after exposure to obtain a resist pattern, a step of etching a resist underlayer film with the resist pattern, and a step of processing the semiconductor substrate with the patterned resist underlayer film Manufacturing method,
As a twelfth aspect, a step of forming an organic layer on a semiconductor substrate, and a resist underlayer film forming composition according to any one of the first to ninth aspects are applied thereon to form a resist underlayer film. A step of curing the resist underlayer film by irradiating the resist underlayer film with an electron beam, a step of forming a resist film thereon, a step of forming a resist pattern by exposure and development, and forming a resist underlayer film by the resist pattern A method of manufacturing a semiconductor device, including a step of etching, a step of etching an organic layer with a patterned resist underlayer film, a step of processing a semiconductor substrate with the patterned organic layer,
As a thirteenth aspect, the method for manufacturing a semiconductor device according to any one of the tenth aspect to the twelfth aspect, wherein the semiconductor substrate is a semiconductor substrate having a hole having an aspect ratio expressed by height / diameter of 1 or more, And as a fourteenth aspect, there is provided the method for manufacturing a semiconductor device according to any one of the tenth aspect to the thirteenth aspect, wherein the electron beam irradiation is performed in the range of 1 to 300 kGy as an absorbed dose.

  With the resist underlayer film forming composition of the present invention, it is possible to form an excellent resist underlayer film by electron beam irradiation, which has a higher dry etching rate than a photoresist and does not cause intermixing with the photoresist. it can.

  It can also be used for a resist underlayer film in which the resist underlayer film has a hard mask function during substrate processing. That is, by using a large amount of an aromatic compound having a high carbon content so as to reduce the dry etching resistance rate, a resist underlayer film having a hard mask function having a slower dry etching rate than a photoresist can be obtained.

  In addition, the resist underlayer film forming composition of the present invention can planarize the surface of a semiconductor substrate having holes having an aspect ratio of 1 or more represented by height / diameter. Therefore, the uniformity of the film thickness of a photoresist or the like applied and formed thereon can be increased. Even in a process using a substrate having holes, a good photoresist pattern can be formed.

  With the resist underlayer film forming composition of the present invention, holes formed in the semiconductor substrate can be filled with the resist underlayer film without generating voids.

Moreover, the resist underlayer film forming composition of this invention can harden and form a resist underlayer film by electron beam irradiation, without heating at high temperature, after apply | coating on a semiconductor substrate. Therefore, contamination of peripheral devices due to volatilization or sublimation of low molecular weight components can be prevented. When sublimation occurs, the sublimation adheres to the processing apparatus, and the sublimation forms a lump, which falls as a foreign substance on the semiconductor substrate and causes a defect in the semiconductor product. However, the resist underlayer film of the present invention does not require heating at a high temperature after being applied to a semiconductor substrate, and is formed by curing the resist underlayer film by electron beam irradiation after heating to the extent that the solvent is removed. Therefore, the above-mentioned problem that causes generation of sublimates does not occur.
In addition, since heating at a high temperature is not required, there is no concern about sublimation even if a low molecular weight component is used in the resist underlayer film forming composition, and a relatively large amount of low molecular weight component is used in the resist underlayer film forming composition. Can be used for Therefore, a resist underlayer film can be formed using a resist underlayer film forming composition having a relatively low viscosity. Then, it is possible to form a resist underlayer film having excellent hole filling properties and semiconductor substrate planarization properties.

  The present invention is a composition for forming a resist underlayer film used as a lower layer of a photoresist by electron beam irradiation in a lithography process for manufacturing a semiconductor device, and is a resist underlayer film forming composition containing a polymerizable substance. .

  The resist underlayer film forming composition of the present invention contains a polymerizable substance and a solvent, and the solid content can be used in the range of, for example, 0.5 to 50% by mass, or 3 to 40% by mass, or 10 to 30% by mass. . The solid content is all remaining components obtained by removing the solvent from the resist underlayer film forming composition.

    The polymerizable substance (A) is a substance having at least one reactive group polymerizable by electron beam irradiation.

The polymerizable compound (A) is an organosilicon compound containing a polymerizable organic group, a hydrolyzate of an organosilicon compound containing a polymerizable organic group, a condensate of a hydrolyzate of an organosilicon compound containing a polymerizable organic group, or A mixture of them.
The reactive group polymerizable by electron beam irradiation is a reactive group having an unsaturated multiple bond between carbon and carbon, or a reactive group having an epoxy group.
The reactive group having an unsaturated multiple bond between carbon and carbon is a reactive group containing a carbon-carbon double bond and a carbon-carbon triple bond, but a carbon-carbon double bond is preferably used. .

Examples of the reactive group containing a carbon-carbon double bond include an acrylate group, a methacrylate group, and a vinyl ether group.
By irradiating the resist underlayer film containing the polymerizable compound (A) with an electron beam, the polymerization of the polymerizable compound (A) proceeds and a resist underlayer film is formed. When the polymerizable compound (A) is a polymerizable compound having at least one epoxy group, the resist underlayer film obtained from the polymerizable compound (A) is irradiated with an electron beam, whereby the polymerizable compound (A ) And the resist underlayer film is formed. When the reactive group is an epoxy group, two or more epoxy groups that are polymerizable sites are preferably contained in the polymerizable compound (A) from the viewpoint of solvent resistance to the solvent of the photoresist to be overcoated.

  In addition, when the polymerizable compound (A) is a polymerizable compound having at least one ethylenically unsaturated bond, the resist underlayer film obtained from the polymerizable compound (A) is irradiated with an electron beam to be polymerizable. Polymerization of compound (A) proceeds and a resist underlayer film is formed. The ethylenically unsaturated bond is preferably a vinyl group. As the vinyl group, an acryloxy group or an organic group containing a methacryloxy group is preferable. In the case where the polymerizable compound (A) is a condensate, it is preferable in terms of solvent resistance to the solvent of the photoresist to be overcoated by having two or more vinyl groups which are polymerizable sites in the condensate.

In the present invention, the polymerizable compound (A) containing a silicon atom is represented by the formula (I):
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (I)
(However, R ¹ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ³ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and R ² is a halogen atom or a carbon number of 1 to 8 is an alkoxy group, an alkoxyalkyl group, or an alkoxyacyl group, a is an integer of 1, b is an integer of 0, 1 or 2, and a + b is an integer of 1, 2 or 3.) and Formula (II):
[(R ⁴ ) _c Si (R ⁵ ) _3-c ] ₂ Y (II)
(However, R ⁴ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ⁵ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and Y is an oxygen atom, a methylene group, or a carbon number of 2 Represents an alkylene group of ˜20, and c is an integer of 1 or 2.) At least one silicon atom selected from the group consisting of an organosilicon compound represented by the following formula, a hydrolyzate thereof, and a condensate thereof: The polymerizable compound (A1) contained can be used.

  Examples of organosilicon compounds of formula (I) corresponding to these polymerizable compounds (A1) include methacrylamide trimethoxysilane, 2-methacryloxyethyltrimethoxysilane, (methacryloxymethyl) bis (trimethyloxy) methylsilane, methacryloxymethyl. Triethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyldimethylchlorosilane, 2-methacryloxyethyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxy Propyltrichlorosilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltripropo Sisilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltris (methoxyethyl) silane, methacryl Roxytrimethoxysilane, methacryloxytributoxysilane, methacryloxytriisopropoxysilane, methacryloxytriphenoxysilane, methacryloxyphenyldimethoxysilane, methacryloxyphenylmethylmethoxysilane, methacryloxyphenyldichlorosilane, methacryloxyphenyldimethylsilane, methacryloxy Loxyphenyldiethoxysilane, methacryloxyphenyldichlorosilane, methacryloxytrimethoxysilane Methacryloxymethyldimethoxysilane, methacryloxymethyldiethoxysilane, methacryloxymethyldiacetoxysilane, methacryloxydiphenylchlorosilane, acrylamidetrimethoxysilane, 2-acryloxyethyltrimethoxysilane, (acryloxymethyl) bis (trimethyloxy) methylsilane, Acryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, 3-acryloxypropyldimethylchlorosilane, 2-acryloxyethyltrimethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3 -Acryloxypropyltrichlorosilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyl Rudimethoxysilane, 3-acryloxypropyltripropoxysilane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxypropyltrimethoxysilane, 3 -Acryloxypropyltris (methoxyethyl) silane, acryloxytrimethoxysilane, acryloxytributoxysilane, acryloxytriisopropoxysilane, acryloxytriphenoxysilane, acryloxyphenyldimethoxysilane, acryloxyphenylmethylmethoxysilane, acryloxy Loxyphenyldichlorosilane, acryloxyphenyldimethylsilane, acryloxyphenyldiethoxysilane, acryloxyphenyldichlorosilane, acrylic Vinyl group-containing silane compounds such as xytrimethoxysilane, acryloxymethyldimethoxysilane, acryloxymethyldiethoxysilane, acryloxymethyldiacetoxysilane, acryloxydiphenylchlorosilane, and glycidoxymethyltrimethoxysilane, glycidoxymethyl Triethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyl Trimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α- Glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ- Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β -(3,4-epoxy (Cyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxy Silane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- ( 3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysila Β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane Silane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropyl Methyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ Preferred examples include epoxy group-containing silane compounds such as glycidoxypropylvinyldiethoxysilane.

  Examples of the organosilicon compound of formula (II) corresponding to the polymerizable compound (A1) include bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane, di (glycidoxypropyl) tetramethyldisiloxane. Epoxy group-containing silane compounds such as di (glycidoxypropyl) tetraphenyldisiloxane, di (3-methacryloxypropyl) tetramethyldisiloxane, di (3-methacryloxypropyl) tetraphenyldisiloxane, di (3- Preferred examples include vinyl group-containing silane compounds such as (acryloxypropyl) tetramethyldisiloxane and di (3-acryloxypropyl) tetraphenyldisiloxane.

  The polymerizable compound (A1) is selected from the group consisting of the organosilicon compounds of the above formulas (I) and (II), the hydrolyzate of the organosilicon compound, and the condensate of the hydrolyzate of the organosilicon compound. It is a polymerizable compound (A1) containing at least one silicon atom.

  In the present invention, for the purpose of improving etching resistance, antireflection properties, storage stability, wettability with a substrate, etc., a polymerizable compound (A1) is added with a silicon atom that does not contain a polymerizable organic group such as an epoxy group and a vinyl group. The polymerizable compound (A2) to be contained can be combined.

The polymerizable compound (A2) containing a silicon atom is represented by the general formula (III),
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (III)
(However, R ¹ and R ³ are each an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group having a mercapto group, an amino group, or a cyano group, and a silicon atom by a Si—C bond. R ² is a halogen atom, or an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an alkoxyacyl group, and a and b are each an integer of 0, 1, or 2. A + b is an integer of 0, 1, or 2) and formula (IV),
[(R ⁴ ) _c Si (X) _3−c ] ₂ Y (IV)
(However, R ⁴ represents an alkyl group having 1 to 5 carbon atoms, X represents an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkyl group or an alkoxyacyl group, and Y represents a methylene group or an alkylene having 2 to 20 carbon atoms. A group containing at least one silicon atom selected from the group consisting of an organosilicon compound represented by the following formula: c is an integer of 0 or 1; a hydrolyzate thereof; and a condensate thereof. is there.
Examples of the organosilicon compound of the formula (III) corresponding to the polymerizable compound (A2) include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraacetoxysilane, Methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltri Methoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro Propyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloro Methyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxy Silane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ Preferred examples include -mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like.

Preferred examples of the organosilicon compound of formula (IV) corresponding to this polymerizable compound (A2) include methylene bismethyldimethoxysilane, ethylene bisethyldimethoxysilane, propylene bisethyldiethoxysilane, butylene bismethyldiethoxysilane, and the like. can do.
The polymerizable compound (A2) is selected from the group consisting of the organosilicon compounds of the above formulas (III) and (IV), the hydrolyzate of the organosilicon compound, and the condensate of the hydrolyzate of the organosilicon compound. It is a polymerizable compound (A2) containing at least one silicon atom.

In the present invention, the polymerizable compound (A) containing the silicon atom is composed of the above (A1) or a combination of the above (A1) and (A2). A condensate having a polymerizable organic group having a weight average molecular weight of 100 to 100,000 obtained by hydrolyzing an organosilicon compound and condensing it at a ratio of (A1) :( A2) of 100: 0 to 50 is preferable.
When hydrolyzing and condensing the organosilicon compound, it is more than 1 mole and less than or equal to 100 moles, preferably 1 mole to 50 moles per mole of hydrolyzable group (for example, chlorine atom or alkoxy group) of the organosilicon compound. Use water.
In producing the polymerizable compound (A) of the present invention, a catalyst is used when hydrolyzing and condensing at least one silane compound selected from the above compounds. Examples of the catalyst that can be used in this case include metal chelate compounds such as titanium and aluminum, acid catalysts, and alkali catalysts.

The polymerizable compound (A) containing the silicon atom has a value of (a + b) of 1 in the organosilicon compound composed of the above formula (I) or a combination of the above formula (I) and the formula (III). A condensate having a polymerizable organic group having a weight average molecular weight of 100 to 1,000,000 obtained by hydrolyzing and condensing an organosilicon compound containing 5 to 75% by mass of the organosilicon compound is preferable.
The resist underlayer film forming composition of the present invention is usually formed by dissolving or dispersing the polymerizable compound (A) in an organic solvent. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.
The resist underlayer film forming composition of the present invention further comprises components such as β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, triazene compound, and alkali compound. It may be added.
The organosilicon compound used in the present invention is usually hydrolyzed and condensed in an organic solvent.
Examples of the organic solvent used for the hydrolysis include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di -Aromatic hydrocarbon solvents such as i-propyl benzene, n-amyl naphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pe Tanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, Heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol , Monoalcohol solvents such as cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2 , 4, 2-ethylhexanediol-1,3, polyhydric alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n -Butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methyl Ketone solvents such as clohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, Ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n -Hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dib Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether Ether solvents such as ter, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, acetic acid Methyl cyclohexyl, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, acetic acid Ethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene acetate Glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, lactate n -Ester solvents such as butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, Nitrogen-containing solvents such as N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide And sulfur-containing solvents such as thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone.
In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate is preferred from the viewpoint of storage stability of the solution.

  A catalyst may be used when the organosilicon compound is hydrolyzed and condensed. Examples of the catalyst used at this time include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di- i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, and other titanium chelate compounds; triethoxy mono (acetylacetonato) zirconium, tri- n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-s c-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconi Mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonate) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethylacetoa Cetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec- Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono -I-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirco , Mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum; Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid , Butyric acid, melicic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, Examples thereof include diazabicycloundecene and tetramethylammonium hydroxide. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

  Furthermore, in order to improve resist adhesion, wettability to the base substrate, flexibility, flatness, etc., the following polymerizable compound containing no silicon atom is used, if necessary, and the above polymerizable compound containing a silicon atom Can be copolymerized (hybridized) or mixed.

Specific examples of the polymerizable compound that does not contain a silicon atom and has an ethylenically unsaturated bond include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] pro 3-phenoxy-2-propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Glycerol tri (meth) acrylate, tris- (2-hydroxylethyl) -isocyanuric acid ester (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (Meth) acrylate etc. are mentioned. Here, for example, ethylene glycol di (meth) acrylate means ethylene glycol diacrylate and ethylene glycol dimethacrylate.
Examples of the polymerizable compound that does not contain a silicon atom and has an ethylenically unsaturated bond include urethane compounds, polyvalent epoxy compounds, and hydroxy compounds that can be obtained by reacting a polyvalent isocyanate compound with a hydroxyalkyl unsaturated carboxylic acid ester compound. Mention may also be made of compounds obtainable by reaction with alkyl unsaturated carboxylic acid ester compounds, diallyl ester compounds such as diallyl phthalate, and divinyl compounds such as divinyl phthalate.
Moreover, as a polymeric compound which does not contain a silicon atom and has a cation polymerizable site | part, the compound which has cyclic ether structures, such as an epoxy ring and an oxetane ring, a vinyl ether structure, a vinyl thioether structure, etc. is mentioned.

  Although there is no restriction | limiting in particular as a polymeric compound which does not contain a silicon atom and has an epoxy ring, The compound which has 1 thru | or 6, and 2 thru | or 4 epoxy rings can be used. As the polymerizable compound having an epoxy ring, for example, it is produced from a compound having two or more hydroxyl groups or carboxyl groups such as a diol compound, a triol compound, a dicarboxylic acid compound and a tricarboxylic acid compound, and a glycidyl compound such as epichlorohydrin. And a compound having two or more glycidyl ether structures or glycidyl ester structures.

  Specific examples of the polymerizable compound that does not contain a silicon atom and has an epoxy ring include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl. Ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′- Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p-aminophenol, tetraglycidyl meta Syrenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S-diglycidyl ether, pentaerythritol tetraglycidyl ether resorcinol diglycidyl ether, diglycidyl phthalate Ester, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, tris- (2,3-epoxypropyl) isocyanate Nurate, monoallyl diglycidyl isocyanurate, diglycerol Diglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-he Xanthdiol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether, 1,2,7, 8-diepoxyoctane, 1,6-dimethylol perfluorohexane diglycidyl ether, 4,4′-bis (2,3-epoxypro Poxyperfluoroisopropyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3,4-epoxycyclohexyl) -3 ′, 4′-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), bis- (3,4-epoxycyclohexylmethyl) Adipate And bis (2,3-epoxy cyclopentyl) ether, and the like.

  Although there is no restriction | limiting in particular as a polymeric compound which does not contain a silicon atom and has an oxetane ring, The compound which has 1 thru | or 6 or 2 thru | or 4 oxetane rings can be used.

  Examples of the polymerizable compound which does not contain a silicon atom and has an oxetane ring include, for example, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3,3-diethyloxetane, and 3-ethyl. -3- (2-ethylhexyloxymethyl) oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, di ((3-ethyl-3-oxetanyl) methyl) ether, And pentaerythritol tetrakis ((3-ethyl-3-oxetanyl) methyl) ether.

  The polymerizable compound having no vinyl atom and having a vinyl ether structure is not particularly limited, and compounds having 1 to 6, or 2 to 4 vinyl ether structures can be used.

  Examples of the polymerizable compound having no vinyl atom and having a vinyl ether structure include vinyl-2-chloroethyl ether, vinyl-normal butyl ether, 1,4-cyclohexanedimethanol divinyl ether, vinyl glycidyl ether, bis (4- (vinyl Roxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4 -(Vinyloxy) butyl isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene Recall divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tri Examples include vinyl ether and cyclohexane dimethanol divinyl ether.

  In the resist underlayer film forming composition of the present invention, in addition to the polymerizable compound (A), a surfactant, a polymer compound, an antioxidant, a thermal polymerization inhibitor, a surface modifier, and a defoamer as necessary. An agent or the like can be added.

  By adding a surfactant, it is possible to suppress the occurrence of pinholes and installations and to improve the applicability of the resist underlayer film forming composition. Examples of the surfactant include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether and the like. Oxyethylene alkyl allyl ether compounds, polyoxyethylene / polyoxypropylene block copolymer compounds, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, sorbitan trisoleate and other sorbitan fatty acid ester compounds, polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxye Polyoxyethylene sorbitan fatty acid ester compounds such as alkylene sorbitan monostearate and polyoxyethylene sorbitan tristearate and the like. In addition, trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 Fluorosurfactants and organosiloxane polymers such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be raised. When a surfactant is used, the addition amount is, for example, 0.1 to 5 parts by mass or 0.5 to 2 parts by mass with respect to 100 parts by mass of the polymerizable compound (A). .

  There is no restriction | limiting in particular as a high molecular compound, The various polymer compound whose weight average molecular weight is about 1000-1 million can be used. Examples thereof include acrylate polymers, methacrylate polymers, novolak polymers, styrene polymers, polyamides, polyamic acids, polyesters and polyimides having a benzene ring, naphthalene ring or anthracene ring.

  In the lithography process for manufacturing a semiconductor device, a polymer compound having excellent light absorption performance used for the antireflection film under the photoresist can also be used. By using such a polymer compound, the performance of the resist underlayer film formed from the resist underlayer film forming composition of the present invention as an antireflection film can be enhanced.

  When a high molecular compound is used, the addition amount is, for example, 0.1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound (A).

The resist underlayer film forming composition of the present invention is a solution in which the polymerizable compound (A) or a component arbitrarily added to the polymerizable compound (A) (both are referred to as a solid content) is dissolved in a solvent (B). It is preferably used in the state. The solid content is the remaining component excluding the solvent in the resist underlayer film forming composition.
As the solvent, any solvent can be used as long as it can dissolve a solid content to form a uniform solution. When the organosilicon compound is hydrolyzed to obtain a condensate and used as the polymerizable compound (A), the organic solvent used for hydrolysis of the organosilicon compound is used as it is as the solvent (B) of the resist underlayer film forming composition. It is preferable.

  Examples of the solvent (B) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl. Ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methoxypropio Methyl acid, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-dimethylformamide, N -Dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and the like can be mentioned.

  These solvent (B) can be used individually or in combination of 2 or more types. As the solvent, a solvent having a boiling point of 80 to 250 ° C, 100 to 200 ° C, or 120 to 180 ° C is preferably used. When the boiling point of the solvent is low, a large amount of the solvent evaporates during the application of the resist underlayer film forming composition, resulting in an increase in viscosity and a decrease in applicability. When the boiling point of the solvent is high, it can be considered that time is required for drying after the application of the resist underlayer film forming composition. The solvent can be used in such an amount that the concentration of the solid content of the resist underlayer film forming composition is, for example, 0.5 to 50% by mass, or 3 to 40% by mass, or 10 to 30% by mass.

In the present invention, a semiconductor device includes a step of applying a resist underlayer film forming composition of the present invention on a semiconductor substrate to form a coating film, and a step of forming a resist underlayer film by irradiating the coating film with an electron beam. Manufactured.
A step of applying a resist underlayer film forming composition of the present invention on a semiconductor substrate to form a coating film; a step of forming a resist underlayer film by irradiating the coating film with an electron beam; A step of forming a photoresist by applying and heating a resist composition, a step of exposing a semiconductor substrate coated with the resist underlayer film and the photoresist, a step of developing the photoresist after exposure to obtain a resist pattern, A semiconductor device is manufactured including a step of etching the resist underlayer film with the resist pattern and a step of processing the semiconductor substrate with the patterned photoresist and the resist underlayer film.

A step of forming an organic film with a coating type organic film forming composition on a semiconductor substrate, a step of forming a resist underlayer film with a resist underlayer film forming composition of the present invention on the semiconductor substrate by electron beam irradiation, and a resist film thereon A step of forming, a step of forming a resist pattern by exposure and development, a step of etching a resist underlayer film by a resist pattern, a step of etching an organic film by a patterned resist underlayer film, and a semiconductor by a patterned organic film A semiconductor device is manufactured including a step of processing the substrate.
The semiconductor substrate is a semiconductor substrate having holes having an aspect ratio of 1 or more represented by height / diameter.

  Hereinafter, the use of the resist underlayer film forming composition of the present invention will be described.

  Semiconductor substrates used for manufacturing semiconductor devices (eg, silicon / silicon dioxide coated substrates, silicon wafer substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, low dielectric constant material (low-k material) coated substrates) Etc.), the resist underlayer film forming composition of the present invention is applied by an appropriate coating method such as a spinner or a coater to form a coating film. And before performing an electron beam irradiation to a coating film, a drying process can be put as needed. When a resist underlayer film forming composition containing a solvent is used, a drying step is preferably performed.

The drying process is not particularly limited unless it is a method of heating at a high temperature. This is because when heated at a high temperature (for example, a temperature of 150 ° C. or higher), sublimation or the like of the solid content contained in the coating film occurs, which may contaminate the apparatus. When such sublimation occurs, the inside of the processing apparatus is contaminated, and a sublimated mass adhering to the processing apparatus falls on the semiconductor substrate, and the falling object may cause a foreign matter and cause a semiconductor defect. In the present invention, such a problem does not occur because the resist underlayer film is cured and formed by electron beam irradiation after the resist underlayer film is applied and then dried.
The said drying process can be performed by heating a board | substrate at 50-100 degreeC for 0.1 to 10 minutes on a hotplate, for example. For example, it can carry out by air-drying at room temperature (about 20 degreeC).

  Next, electron beam irradiation is performed on the applied resist underlayer film. For the electron beam irradiation, any method that can act on the electron beam polymerization compound and cause polymerization of the polymerizable substance can be used without particular limitation. The electron dose to be irradiated is preferably adjusted in the range of about 1 to 300 kGy as an absorbed dose. If it is less than 1 kGy, sufficient irradiation effect cannot be obtained, and irradiation exceeding 300 kGy is not preferable because there is a possibility of deteriorating the substrate. As an electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like is used. The acceleration voltage when irradiating an electron beam needs to be controlled by the thickness of the substrate on the irradiation side. However, about 20 to 100 kV is appropriate.

  Electron beam irradiation generates cationic species and active radicals from the electron beam polymerization compound in the coating film, and these cause a polymerization reaction of the polymerizable substance in the coating film. Radical polymerization having an addition polymerizable unsaturated bond in the electron beam polymerization compound occurs by electron beam irradiation. As a result of this polymerization reaction, a resist underlayer film is formed. The resist underlayer film thus formed is a solvent used in the photoresist composition applied to the upper layer, such as ethylene glycol monomethyl ether, ethyl cellosolve acetate, diethylene glycol monoethyl ether, propylene glycol, propylene. Glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl pyruvate, ethyl lactate In addition, the solubility in butyl lactate and the like is low. For this reason, the resist underlayer film formed from the resist underlayer film forming composition of the present invention does not cause intermixing with the photoresist.

  The resist underlayer film forming composition of the present invention can be applied to a semiconductor substrate having holes having an aspect ratio of 1 or more, for example, 1 to 10, or 2 to 5, as shown in FIG. it can. The resist underlayer film forming composition of the present invention can be used for filling such holes with a resist underlayer film without generating voids. Further, the resist underlayer film forming composition of the present invention can be applied to a semiconductor substrate (a substrate having a portion where holes are densely and sparsely present) having holes having an aspect ratio of 1 or more. it can. And the resist underlayer film forming composition of this invention can be used in order to form a flat resist underlayer film on the surface of the board | substrate in which such a hole exists densely.

  The resist underlayer film forming composition of the present invention can also be used for a semiconductor substrate having holes with an aspect ratio smaller than 1 and a semiconductor substrate having steps. It can also be used for a semiconductor substrate having no step.

  The film thickness of the resist underlayer film formed from the resist underlayer film forming composition of the present invention is, for example, 20 to 2000 nm, 30 to 1000 nm, or 50 to 800 nm on the substrate surface.

  Next, a photoresist is formed on the resist underlayer film. As a result, a laminated structure of the resist underlayer film and the photoresist is formed on the semiconductor substrate. The formation of the photoresist can be performed by a well-known method, that is, by applying a photoresist composition solution onto the resist underlayer film and heating. There is no restriction | limiting in particular as a photoresist formed on the resist underlayer film of this invention, Both the negative type photoresist and the positive type photoresist which are used widely can be used. For example, a positive photoresist comprising a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, Chemically amplified photoresist comprising a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, a binder having a group that decomposes with acid to increase the alkali dissolution rate And chemically amplified photoresists composed of a low molecular weight compound that decomposes with acid and increases the alkali dissolution rate of the photoresist and a photoacid generator, such as the trade name APEX-E manufactured by Shipley Co., Ltd., Sumitomo Chemical Co., Ltd. ) Product name PAR710, Shin-Etsu Chemical Co., Ltd. product name SEPR It includes the 30 or the like.

  Next, exposure is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), or the like can be used. After exposure, post-exposure bake can be performed as necessary. The post-exposure heating is appropriately selected from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 to 10 minutes.

  Next, development is performed with a developer. Thus, for example, when a positive photoresist is used, the exposed portion of the photoresist is removed, and a photoresist pattern is formed.

  Developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, propylamine, An alkaline aqueous solution such as an aqueous amine solution such as ethylenediamine can be mentioned as an example. Further, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50 ° C. and a time of 0.1 to 5 minutes.

Then, using the photoresist pattern thus formed as a protective film, the resist underlayer film is removed and the semiconductor substrate is processed. Removal of the resist underlayer film includes tetrafluoromethane, perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoro It can be performed by dry etching using a gas such as methane, nitrogen trifluoride, and chlorine trifluoride. By removing the resist underlayer film, a pattern composed of the resist underlayer film and the photoresist is formed on the semiconductor substrate.

  Further, an antireflection film layer can be formed on the resist underlayer film of the present invention before forming the photoresist. The antireflection film is not particularly limited, and an existing antireflection film can be used, and an organic antireflection film, a silicon-containing inorganic antireflection film, or an antireflection film in which organic and inorganic are hybridized is used. Can do. For example, by using a composition for forming an antireflection film conventionally used in a lithography process, the antireflection film can be formed by a conventional method, for example, application on a resist underlayer film by a spinner or a coater, and baking. Formation can be performed. Examples of the antireflection film composition include a light-absorbing compound, a resin and a solvent as a main component, a resin having a light-absorbing group linked by a chemical bond, a cross-linking agent and a solvent as a main component, and a light-absorbing compound. And those having a cross-linking agent and a solvent as main components and those having a light-absorbing polymer cross-linking agent and a solvent as main components. These anti-reflective coating compositions can also contain an acid component, an acid generator component, a rheology modifier, and the like, if necessary. Any light-absorbing compound can be used as long as it has a high absorption capability for light in the photosensitive characteristic wavelength region of the photosensitive component in the photoresist provided on the antireflection film. Examples include triazole compounds, azo compounds, naphthalene compounds, anthracene compounds, anthraquinone compounds, triazine compounds, and the like. Examples of the resin include polyester, polyimide, polystyrene, novolac resin, polyacetal resin, and acrylic resin. Examples of the resin having a light-absorbing group linked by a chemical bond include resins having a light-absorbing aromatic ring structure such as an anthracene ring, naphthalene ring, benzene ring, quinoline ring, quinoxaline ring, and thiazole ring.

  In addition, before applying the resist underlayer film forming composition of the present invention, an antireflection film or a planarizing film can be formed on the semiconductor substrate.

  The resist underlayer film formed from the resist underlayer film forming composition of the present invention may have absorption of light depending on the wavelength of light used in the lithography process. In such a case, it can function as a layer having an effect of preventing reflected light from the substrate, that is, an antireflection film. Furthermore, the resist underlayer film of the present invention prevents the adverse effect on the semiconductor substrate of the layer for preventing the interaction between the substrate and the photoresist, the material used for the photoresist or the substance generated upon exposure to the photoresist. It can also be used as a layer for preventing the diffusion of the material generated from the semiconductor substrate during heating and baking into the upper photoresist.

  In the future, as the miniaturization of the resist pattern progresses, there arises a problem of resolution and a problem that the resist pattern collapses after development, and a thinner photoresist is desired. For this reason, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed functions as a mask during substrate processing. The process to have it has become necessary. Unlike conventional high-etch-rate resist underlayer films as resist underlayer films for such processes, resist underlayer films with a selectivity ratio of dry etching rates close to that of photoresist, and a lower dry etching rate selection than photoresists A resist underlayer film having a high ratio and a resist underlayer film having a selective ratio of a dry etching rate smaller than that of a semiconductor substrate have been demanded. Further, such a resist underlayer film can be provided with an antireflection ability, and can also have a function of a conventional antireflection film.

  In the present invention, after forming the resist underlayer film of the present invention on the substrate, directly or on the resist underlayer film as needed, after forming one to several layers of coating material on the resist underlayer film, Photoresist can be applied. As a result, the pattern width of the photoresist is narrowed, and even when the photoresist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas.

  That is, a step of forming the resist underlayer film on the semiconductor substrate with the resist underlayer film forming composition, a step of forming a hard mask with a coating material containing a silicon component or the like thereon, and further forming a resist film thereon A step of forming a resist pattern by exposure, development, a step of etching a hard mask with a resist pattern, a step of etching the resist underlayer film with a patterned hardmask, and a semiconductor substrate with a patterned resist underlayer film A semiconductor device can be manufactured through the process of processing.

  The resist underlayer film of the present invention has a characteristic that an appropriate dry etching rate that satisfies these requirements can be obtained.

  Furthermore, the resist underlayer film material of the present invention has a function of preventing reflection of light depending on process conditions, and further prevents the interaction between the substrate and the photoresist or exposes the material used for the photoresist or the photoresist. It can be used as a film having a function of preventing an adverse effect on a substrate of a substance sometimes generated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by this.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by this.

Example 1
2.0 g of 3- (acryloxypropyl) trimethoxysilane (manufactured by Azmax Co., Ltd. molecular weight 234.32), 0.0768 g of water, and 0.147 g of paratoluenesulfonic acid were added to 19.32 g of ethyl lactate, and The mixture was stirred for a period of time to hydrolyze 3- (acryloxypropyl) trimethoxysilane to obtain a condensate thereof.
Next, 0.05 g of a surfactant (manufactured by Dainippon Ink and Chemicals, trade name Megafak R30) was added to the solution, and the mixture was adjusted to a 10% by mass solution in ethyl lactate. Then, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a resist underlayer film forming composition solution.

(Elution test for photoresist solvent)
The solution of the resist underlayer film-forming composition obtained in Example 1 was subjected to a semiconductor substrate (Tokyo Electron, trade name CLEANTRACK ACT-8 ^TM hexamethyldisilazane (HMDS) treatment apparatus using a HMDS atmosphere as an adhesion aid. On a silicon wafer substrate hydrophobized by a vapor method soaked in the substrate for 60 seconds to form a coating film. The coating film was subjected to an accelerating voltage of 100 kV, a current value of 3.52 mA, a K value of 14.6, an irradiation dose of 50.0 kGy using an electron beam irradiation apparatus (model CB250 / 15 / 180L manufactured by I. Electron Beam Co., Ltd.). Irradiation was performed under the following conditions. Then, in order to remove the solvent and dry it, it was heated on a hot plate at 130 ° C. for 1 minute to form a resist underlayer film (film thickness 182 nm). These resist underlayer films were immersed in ethyl lactate, which is a solvent used for photoresist, and confirmed to be insoluble in these solvents.

(Test of intermixing with photoresist)
In the same manner as described above, an adhesive aid was prepared using a solution of the resist underlayer film forming composition obtained in Example 1 with a semiconductor substrate (trade name CLEANTRACK ACT-8 ^TM, a hexamethyldisilazane (HMDS) treatment apparatus. A resist underlayer film (film thickness: 182 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. A photoresist solution (trade name APEX-E, manufactured by Shipley Co., Ltd.) was applied to the upper layer of the resist underlayer film by a spinner. A photoresist was formed by baking at 90 ° C. for 1 minute on a hot plate. Then, after exposing the photoresist, post-exposure heating was performed at 90 ° C. for 1.5 minutes. After developing the photoresist, the thickness of the resist underlayer film was measured, and it was confirmed that no intermixing occurred between the resist underlayer film and the photoresist.

(Measurement of optical parameters)
In the same manner as described above, from the solution of the resist underlayer film forming composition obtained in Example 1, a semiconductor substrate (manufactured by Tokyo Electron, trade name CLEANTRACK ACT-8 ^{TM with} a hexamethyldisilazane (HMDS) treatment apparatus was used as an adhesive aid. A resist underlayer film (film thickness 182 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed for 60 seconds in a certain HMDS atmosphere, and electron beam irradiation was performed under the same conditions as described above. The refractive index (n value) and attenuation coefficient (k value) at a wavelength of 193 nm of the resist underlayer film were measured with a spectroscopic ellipsometer. The refractive index was 1.61 and the attenuation coefficient was 0.14. It was.

(Dry etching rate test)
In the same manner as described above, from the solution of the resist underlayer film forming composition obtained in Example 1, a semiconductor substrate (manufactured by Tokyo Electron, trade name CLEANTRACK ACT-8 ^{TM with} a hexamethyldisilazane (HMDS) treatment apparatus was used as an adhesive aid. A resist underlayer film (film thickness: 182 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. And using Nihon Scientific RIE system ES401, the dry etching rate (thickness reduction per unit time) of the resist underlayer film is measured under the condition using O ₂ and CF ₄ as dry etching gas. did. The obtained results are shown as the selectivity of the dry etching rate. The ratio of the dry etching rate of the resist underlayer film when the dry etching rate under the same conditions of a photoresist for KrF laser lithography (trade name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.) is 1.00 is shown. This is the selection ratio of the dry etching rate.
As a dry etching gas, the selection ratio of the etching rate of O ₂ is 0.06 and is hardly etched, and the selection ratio of the etching rate of CF ₄ is 1.6.

Example 2
10.0 g of vinyltrimethoxysilane (manufactured by Azmax Co., Ltd.), 0.605 g of water, and 1.16 g of paratoluenesulfonic acid were added to 105.9 g of ethyl lactate and stirred at room temperature for 3 hours. Trimethoxysilane was hydrolyzed to obtain a condensate thereof.
Next, 0.20 g of a surfactant (manufactured by Dainippon Ink Chemical Co., Ltd., trade name Megafac R30) was added, and the mixture was adjusted to a 10% by mass solution in ethyl lactate. Then, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a resist underlayer film forming composition solution.

(Elution test for photoresist solvent)
The solution of the resist underlayer film forming composition obtained in Example 2 was applied to a semiconductor substrate (manufactured by Tokyo Electron, trade name CLEAN TRACK ACT-8 ^TM , hexamethyldisilazane (HMDS) treatment apparatus using HMDS as an adhesion aid. A coating film was formed by coating on a silicon wafer substrate (hydrophobic-treated by a vapor method immersed in an atmosphere for 60 seconds). The coating film was subjected to an accelerating voltage of 100 kV, a current value of 3.52 mA, a K value of 14.6, an irradiation dose of 50.0 kGy using an electron beam irradiation apparatus (model CB250 / 15 / 180L manufactured by I. Electron Beam Co., Ltd.). Irradiation was performed under the following conditions. Then, in order to remove the solvent and dry it, it was heated on a hot plate at 130 ° C. for 1 minute to form a resist underlayer film (film thickness 174 nm). These resist underlayer films were immersed in ethyl lactate, which is a solvent used for photoresist, and confirmed to be insoluble in these solvents.

(Test of intermixing with photoresist)
In the same manner as described above, the resist underlayer film forming composition solution obtained in Example 2 was used as an adhesion aid for a semiconductor substrate (CLEAN TRACK ACT-8 ^TM 's hexamethyldisilazane (HMDS) processing apparatus manufactured by Tokyo Electron. A resist underlayer film (film thickness: 174 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. A photoresist solution (trade name APEX-E, manufactured by Shipley Co., Ltd.) was applied to the upper layer of the resist underlayer film by a spinner. A photoresist was formed by baking at 90 ° C. for 1 minute on a hot plate. Then, after exposing the photoresist, post-exposure heating was performed at 90 ° C. for 1.5 minutes. After developing the photoresist, the thickness of the resist underlayer film was measured, and it was confirmed that no intermixing occurred between the resist underlayer film and the photoresist.

(Measurement of optical parameters)
In the same manner as described above, an adhesion aid was prepared from a solution of the resist underlayer film forming composition obtained in Example 2 using a hexamethyldisilazane (HMDS) treatment apparatus manufactured by Tokyo Electron, trade name CLEAN TRACK ACT-8 ^TM. A resist underlayer film (film thickness 174 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. It was. The refractive index (n value) and attenuation coefficient (k value) at a wavelength of 193 nm of the resist underlayer film were measured by a spectroscopic ellipsometer. The refractive index was 1.63 and the attenuation coefficient was 0.06. It was.

(Dry etching rate test)
In the same manner as described above, an adhesion aid was prepared from a solution of the resist underlayer film forming composition obtained in Example 2 using a hexamethyldisilazane (HMDS) treatment apparatus manufactured by Tokyo Electron, trade name CLEAN TRACK ACT-8 ^TM. A resist underlayer film (film thickness: 174 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. And using Nihon Scientific RIE system ES401, the dry etching rate (thickness reduction per unit time) of the resist underlayer film is measured under the condition using O ₂ and CF ₄ as dry etching gas. did. The obtained results are shown as the selectivity of the dry etching rate. The ratio of the dry etching rate of the resist underlayer film when the dry etching rate under the same conditions of a photoresist for KrF laser lithography (trade name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.) is 1.00 is shown. This is the selection ratio of the dry etching rate.
As a dry etching gas, the selection ratio of the etching rate of O ₂ is 0.05 and hardly etched, and the selection ratio of the etching rate of CF ₄ is 1.6.

Example 3
2.0 g of vinylmethylsiloxane-dimethylsiloxane copolymer (VDT-731 trimethylsiloxane end, manufactured by Azmax Co., Ltd.), 5.723 g of cyclohexanone, 5.723 g of propylene glycol monomethyl ether acetate, and a surfactant (Dainippon Ink Chemical Co., Ltd.) ), Trade name Megafak R30) 0.20 g was added to prepare a 15% by mass solution. Then, the solution was filtered using a polyethylene microfilter having a pore size of 0.2 μm to prepare a resist underlayer film forming composition solution.

(Elution test for photoresist solvent)
The solution of the resist underlayer film forming composition obtained in Example 3 was applied to a semiconductor substrate (trade name CLEAN TRACK ACT-8 ^TM , hexamethyldisilazane (HMDS) treatment apparatus by using a spinner, and HMDS as an adhesion aid. A coating film was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. The coating film was subjected to an accelerating voltage of 100 kV, a current value of 3.52 mA, a K value of 14.6, an irradiation dose of 50.0 kGy using an electron beam irradiation apparatus (model CB250 / 15 / 180L manufactured by I. Electron Beam Co., Ltd.). Irradiation was performed under the following conditions. And in order to remove and dry a solvent, it heated on 130 degreeC on the hotplate for 1 minute, and formed the resist lower layer film (film thickness of 219 nm). These resist underlayer films were immersed in ethyl lactate, which is a solvent used for photoresist, and confirmed to be insoluble in these solvents.

(Test of intermixing with photoresist)
In the same manner as described above, a solution of the resist underlayer film forming composition obtained in Example 3 was used to bond an adhesion aid using a hexamethyldisilazane (HMDS) treatment apparatus manufactured by Tokyo Electron, trade name CLEAN TRACKACT-8 ^TM. A resist underlayer film (thickness: 219 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. A photoresist solution (trade name APEX-E, manufactured by Shipley Co., Ltd.) was applied to the upper layer of the resist underlayer film by a spinner. A photoresist was formed by baking at 90 ° C. for 1 minute on a hot plate. Then, after exposing the photoresist, post-exposure heating was performed at 90 ° C. for 1.5 minutes. After developing the photoresist, the thickness of the resist underlayer film was measured, and it was confirmed that no intermixing occurred between the resist underlayer film and the photoresist.

(Measurement of optical parameters)
In the same manner as described above, an adhesion aid was prepared from a solution of the resist underlayer film forming composition obtained in Example 3 using a hexamethyldisilazane (HMDS) treatment apparatus manufactured by Tokyo Electron, trade name CLEAN TRACK ACT-8 ^TM. A resist underlayer film (film thickness 219 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. Then, when the refractive index (n value) and attenuation coefficient (k value) at a wavelength of 193 nm of the resist underlayer film were measured by a spectroscopic ellipsometer, the refractive index was 1.58 and the attenuation coefficient was 0.09. It was.

(Dry etching rate test)
In the same manner as described above, an adhesion aid was prepared from a solution of the resist underlayer film forming composition obtained in Example 3 using a hexamethyldisilazane (HMDS) treatment apparatus manufactured by Tokyo Electron, trade name CLEAN TRACK ACT-8 ^TM. A resist underlayer film (thickness: 219 nm) was formed on a silicon wafer substrate hydrophobized by a vapor method immersed in an HMDS atmosphere for 60 seconds, and electron beam irradiation was performed under the same conditions as described above. And using Nihon Scientific RIE system ES401, the dry etching rate (thickness reduction per unit time) of the resist underlayer film is measured under the condition using O ₂ and CF ₄ as dry etching gas. did. The obtained results are shown as the selectivity of the dry etching rate. The ratio of the dry etching rate of the resist underlayer film when the dry etching rate under the same conditions of a photoresist for KrF laser lithography (trade name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.) is 1.00 is shown. This is the selection ratio of the dry etching rate.
As the dry etching gas, the selectivity of the etching rate of O ₂ is 0.08, which is hardly etched, and the selectivity of the etching rate of CF ₄ is 1.6.

FIG. 1 is a cross-sectional view of a state in which a resist underlayer film and a photoresist film are formed from a resist underlayer film forming composition of the present invention on a semiconductor substrate having holes. FIG. 2 is a cross-sectional view of a state in which an organic film, a resist underlayer film and a photoresist film made of the resist underlayer film forming composition of the present invention are formed on a semiconductor substrate having holes.

Explanation of symbols

  (1) is a processed substrate.

  (2) is an organic film.

  (3) is a resist underlayer film by the resist underlayer film forming composition of the present invention.

  (4) is a photoresist film.

  (A) is the diameter of the hole.

  (B) is the depth of the hole in the used semiconductor substrate.

Claims (7)

A composition for forming, by electron beam irradiation, a resist underlayer film used as a lower layer of a photoresist in a lithography process for manufacturing a semiconductor device, the polymerizable compound (A) containing 5 to 45% by mass of silicon atoms, And a solvent underlayer film-forming composition, wherein the polymerizable compound (A) has the formula (I):
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (I)
(However, R ¹ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ³ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and R ² is a halogen atom or a carbon number of 1 to 8 alkoxy group, an alkoxyalkyl group, or an alkoxy acyl group, a is 1, b is an integer of 0, a + b is an integer of 1. organosilicon compound represented by) and formula (II):
[(R ⁴ ) _c Si (R ⁵ ) _3-c ] ₂ Y (II)
(However, R ⁴ is an epoxy group, a vinyl group, or a polymerizable organic group containing them, which is bonded to a silicon atom by a Si—C bond, and R ⁵ is an alkyl group, an aryl group, or an alkyl halide. An organic group having a group, a halogenated aryl group, a mercapto group, an amino group, or a cyano group, and bonded to a silicon atom by a Si—C bond, and Y is an oxygen atom, a methylene group, or a carbon number of 2 indicates 20 alkylene group, c is an integer of 1 or 2. the organic silicon compound represented by), its these hydrolyzate, and at least selected from that group consisting of those of the condensate The resist underlayer film forming composition, which is a polymerizable compound (A1) containing one kind of silicon atom, is applied on a semiconductor substrate to form a resist underlayer film, and the resist underlayer film has electrons. A method for manufacturing a semiconductor device, comprising a step of curing a resist underlayer film by irradiating with a line. Applying the resist underlayer film forming composition according to claim 1 on a semiconductor substrate to form a resist underlayer film, and curing the resist underlayer film by irradiating the resist underlayer film with an electron beam, A step of forming a photoresist layer by applying a photoresist composition on the resist underlayer film and heating, a step of exposing the semiconductor substrate covered with the resist underlayer film and the photoresist layer, and developing the photoresist after exposure A method of manufacturing a semiconductor device, comprising: obtaining a resist pattern; etching a resist underlayer film with the resist pattern; and processing a semiconductor substrate with the patterned resist underlayer film. A step of forming an organic layer on a semiconductor substrate, a step of applying a resist underlayer film forming composition according to claim 1 thereon to form a resist underlayer film, and irradiating the resist underlayer film with an electron beam A step of curing the resist underlayer film, a step of forming a resist film thereon, a step of forming a resist pattern by exposure and development, a step of etching the resist underlayer film by the resist pattern, and an organic layer by the patterned resist underlayer film A method for manufacturing a semiconductor device, comprising: a step of etching a semiconductor substrate; and a step of processing a semiconductor substrate with a patterned organic layer. 4. The method of manufacturing a semiconductor device according to claim 1, wherein the semiconductor substrate is a semiconductor substrate having holes having an aspect ratio expressed by height / diameter of 1 or more. 5. 5. The method of manufacturing a semiconductor device according to claim 1, wherein the electron beam irradiation is performed in the range of 1 to 300 kGy as an absorbed dose. Polymerizable compound containing the silicon atom (A) is an organic silicon compound represented by the above organic silicon compound represented by the formula (I) and Formula (II), their these hydrolyzate, and its Re at least one polymerizable compound containing silicon atoms selected from the group consisting of condensates of al the (A1),
General formula (III) :
(R ¹ ) _a (R ³ ) _b Si (R ² ) _{4- (a + b)} (III)
(However, R ¹ and R ³ are each an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, or an organic group having a mercapto group, an amino group, or a cyano group, and a silicon atom by a Si—C bond. R ² is a halogen atom, or an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an alkoxyacyl group, and a and b are each an integer of 0, 1, or 2. And a + b is an integer of 0, 1, or 2.) and an organic silicon compound represented by formula (IV) :
[(R ⁴ ) _c Si (X) _3−c ] ₂ Y (IV)
(However, R ⁴ represents an alkyl group having 1 to 5 carbon atoms, X represents an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkyl group or an alkoxyacyl group, and Y represents a methylene group or an alkylene having 2 to 20 carbon atoms. It represents a group, c is an integer of 0 or 1. organic silicon compound represented by) its at least one silicon these hydrolyzate, and selected from its group consisting of those of the condensate 6. The method for manufacturing a semiconductor device according to claim 1, wherein the semiconductor device is a combination with a compound (A2) containing an atom. The polymerizable compound (A) containing a silicon atom is composed of the above (A1) or a combination of the above (A1) and (A2), and (A1) :( A2) is 100: 0 to 50 in molar ratio. The method for producing a semiconductor device according to any one of claims 1 to 6, wherein the organic silicon compound is a condensate having a polymerizable organic group having a weight average molecular weight of 100 to 100,000 obtained by hydrolyzing and condensing the resulting organosilicon compound. .

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