CN100547487C - Composition for forming antireflection film for photolithography - Google Patents

Abstract

The present invention provides a composition for forming an anti-reflection film, which is used to exhibit good light absorption to light of a wavelength used in the manufacture of semiconductor devices, has a high anti-reflection light effect, and is compatible with a photoresist Layers have a larger etch rate compared to organic anti-reflective coatings. Specifically, the present invention provides an antireflection film-forming composition characterized by containing a triazinetrione compound, an oligomer compound or a high molecular compound having a hydroxyalkyl structure as a substituent on a nitrogen atom.

Description

Composition for forming antireflection film for photolithography

technical field

The present invention relates to a composition for anti-reflection film materials, in particular to a composition for forming an anti-reflection film, which reduces the amount of photoinduced radiation applied to a substrate in the photolithography process of semiconductor device manufacturing. The exposure of the resist layer is irradiated by the reflection of light from the substrate. More specifically, it relates to a composition for forming an antireflection film, which contains a reflective material that effectively absorbs reflection reflected from a substrate in a photolithography process for semiconductor device manufacturing using exposure reflected light having a wavelength of 248nm, 193nm or 157nm. Light compounds, oligomers or polymer compounds.

Background technique

Conventionally, in the manufacture of semiconductor devices, microfabrication has been performed by photolithography using a photoresist composition. The above-mentioned microfabrication is to form a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, and to irradiate active light rays such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn on the thin film for development, A processing method in which a semiconductor substrate is etched using the obtained photoresist pattern as a protective film. However, in recent years, the high integration of semiconductor devices has been continuously developed, and the active light used has a tendency to be shortened by switching from i-line (wavelength 365nm) and KrF excimer laser (wavelength 248nm) to ArF excimer laser (wavelength 193nm) . Along with this, the diffuse reflection of active light from the semiconductor substrate and the influence of standing waves have gradually become major problems. Therefore, the method of providing an anti-reflection film (Bottom Anti-reflective Coating: BARC) between the photoresist and the semiconductor substrate has been widely studied.

As the antireflection film, inorganic antireflection films such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and α-silicon, and organic antireflection films containing a light-absorbing substance and a polymer compound are known. While the former requires equipment such as a true vapor deposition device, CVD device, and sputtering device when forming a film, the latter is advantageous in that it does not require special equipment, and has been extensively studied. For example, an acrylic resin type antireflection film having a hydroxyl group as a crosslinking reactive group and a light absorbing group in the same molecule, and a novolac type novolak having a hydroxyl group as a crosslinking reactive group and a light absorbing group in the same molecule Resin type antireflection film etc. (For example, refer patent document 1, patent document 2).

The physical properties required as an organic anti-reflection film material are high absorbance to light or radiation, no mixing with the photoresist layer (insoluble in photoresist solvents), and drying after coating or heating When there is no diffusion of low-molecular diffusers from the anti-reflection film material to the resist coated thereon, it has a dry etching rate greater than that of photoresists (for example, refer to Non-Patent Document 1, Non-Patent Document 1, Non-Patent Document 1, etc. Document 2, non-patent document 3).

In recent years, in photolithography processes using KrF excimer lasers and ArF excimer lasers, miniaturization of processing dimensions, that is, miniaturization of the size of photoresist patterns to be formed has gradually progressed. Along with the development of miniaturization of photoresist patterns, in order to prevent the collapse of photoresist patterns, etc., it is also expected to achieve thinner photoresists. And when photoresist is used as a thin film, in order to suppress the reduction of the film thickness of photoresist layer in the process of removing the photoresist layer by etching of the organic antireflection film used together, people expect to be able to shorten Time to carry out the removal of the organic anti-reflective coating by etching. That is, in order to shorten the time of the etching removal process, an organic antireflection film that can be used as a thin film or an organic antireflection film that has a higher etching rate selectivity ratio to a photoresist than before is required.

However, conventional researches on antireflection film technologies have been mainly conducted on photolithography processes using irradiation light having wavelengths of 365 nm, 248 nm, and 193 nm. In such studies, light-absorbing components and light-absorbing groups that efficiently absorb light of various wavelengths have been developed and utilized as one component of organic antireflection film compositions. For example, regarding the irradiation light of 365nm, it is known that the chalcone dye generated by the condensation of 4-hydroxyacetophenone and 4-methoxybenzaldehyde is effective (for example, refer to Patent Document 3); regarding the irradiation light of 248nm, It is known that a naphthyl group-containing polymer having a specific structure exhibits a large absorbance (for example, refer to Patent Document 4); regarding irradiated light at 193 nm, it is known that a resin adhesive composition containing a phenyl unit is excellent (for example, , refer to Patent Document 5).

In addition, it is known that tris(hydroxyalkyl)isocyanates substituted with aromatic compounds or aliphatic compounds are used in wide-area ultraviolet absorbers (for example, refer to Patent Document 6), and it is known that cyanuric acid is used as A cured composition of a polymerizable organic compound (for example, refer to Patent Document 7). In addition, an antireflection film composition containing a cyanuric acid derivative is also known (for example, refer to Patent Document 8). In addition, it is disclosed that a polyester synthesized from 1,3,5-tris(2-hydroxyethyl)cyanuric acid is used for an antireflection film (for example, refer to Patent Document 9 and Patent Document 10).

In recent years, a photolithography process using light irradiated with an F2 excimer laser (wavelength: 157 nm) as a light source with a shorter wavelength has been proposed as a next-generation technology using an ArF excimer laser (wavelength: 193 nm). It is believed that microfabrication with a processing size of 100nm or less can be carried out by using this process, and active research and development are currently being carried out from the aspects of devices and materials. But the fact is that most of the research on materials is on photoresists, and the research on organic anti-reflective coatings is basically unknown. The reason for this is that a component that effectively absorbs light at a wavelength of 157 nm, that is, a light-absorbing component that has a strong absorption band at 157 nm is basically unknown.

Since it is considered that in the photolithography process using F2 excimer laser (wavelength 157nm) to irradiate light, the processing size will reach 100nm or less. Therefore, starting from the requirements of the aspect ratio, it is considered that the photoresist can be used in accordance with the film thickness. Compared with existing films of 100 to 300 nm, they are used in the form of thin films. An organic antireflection film used together with such a thin-film photoresist is required to be able to be used as a thin film and to have a high selectivity to dry etching of the photoresist. In addition, in order that the organic antireflection film can be used as a thin film of 30 to 80 nm, it is considered that an antireflection film with a large attenuation coefficient k value is required. In the simulation test using PROLITHver.5 (manufactured by LithoTechJapan: the optical constants (refractive index, attenuation coefficient) of the photoresist use the expected ideal values), the following results were obtained: When the base substrate is made of silicon Among them, as an anti-reflection film with a film thickness of 30-80nm, a film whose film thickness is the second minimum film thickness (about 70nm) can be used, and at this time, the attenuation coefficient k value is in the range of 0.3-0.6, which has The reflectance is less than or equal to 2% for sufficient anti-reflection effect. In addition, according to the same simulation test, the following results were obtained: in the case of using silicon oxide as the base substrate and changing the thickness of the silicon oxide film within the range of 100nm to 200nm, when the film thickness of the antireflection film is 70nm, in order to obtain For sufficient anti-reflection effect, the attenuation coefficient k value must be 0.4~0.6. For example, when the value of the attenuation coefficient k is 0.2, the reflectivity of the slave substrate varies between 5% and 10%, and when the value of the attenuation coefficient k is 0.4, the reflectivity of the slave substrate varies between 0 and 5%. In this way, it is considered that in order to obtain a sufficient antireflection effect, the attenuation coefficient k must be a large value, for example, 0.3 or more, but organic antireflection coating materials satisfying such an attenuation coefficient k are basically unknown.

From this fact, it is desired to develop an organic antireflection film that can efficiently absorb reflected light from a substrate even in a photolithography process using irradiation light with a wavelength of 157 nm, and has an excellent antireflective light effect. Furthermore, currently, people are actively researching photoresists for photolithography using irradiation light from an F2 excimer laser, and it is considered that various photoresists will be developed in the future. In addition, it is considered that a method of changing the characteristics of the antireflection film, for example, a method of changing the value of the attenuation coefficient k, in accordance with various required characteristics of such a variety of photoresists has gradually become important.

Patent Document 1: Specification of US Patent No. 5919599

Patent Document 2: Specification of US Patent No. 5,693,691

Patent Document 3: Japanese Patent Publication No. 11-511194

Patent Document 4: Japanese Unexamined Patent Application Publication No. H10-186671

Patent Document 5: JP-A-2000-187331

Patent Document 6: JP-A-11-279523

Patent Document 7: Japanese Unexamined Patent Publication No. H10-204110

Patent Document 8: International Publication No. 02/086624 Pamphlet

Patent Document 9: Specification of European Patent Application Publication No. 1298492

Patent Document 10: Specification of European Patent Application Publication No. 1298493

Non-Patent Document 1: Tom Lynch and three others, "Properties and Performance of Near UV Reflectivity Control Layers", USA, "in Advances in Resist Technology and Processing XI", edited by Omkaram Nalamasu, SPIE Journal, 1994, Vol. 2195, p .225-229

Non-Patent Document 2: G.Taylor and 13 others, "Methacrylate Resist and Antireflective Coatings for 193nm Lithography", USA, "in Microlithography 1999: Advance in Resist Technology and Processing XVI", edited by Will Conley, SPIE Journal, 1999, No. 3678 Volume, p.174-185

Non-Patent Document 3: Jim D. Meador and 6 others, "Recent Progress in 193nm Antireflective Coatings", USA, "in Microlithography 1999: Advances in Resist Technology and Processing XVI", edited by Will Conley, SPIE Journal, 1999, Vol. 3678 , p.800-809

The invention relates to a composition for forming an anti-reflection film for photolithography, which is used for the anti-reflection film. The anti-reflection film has strong absorption for short-wavelength light, especially light with a wavelength of 248nm, 193nm or 157nm. In addition, the present invention provides a composition for forming an anti-reflection film, which can be carried out using irradiation light of a KrF excimer laser (wavelength 248nm), an ArF excimer laser (wavelength 193nm) or an F2 excimer laser (wavelength 157nm). Used in photolithographic processes for semiconductor device fabrication. In addition, the present invention provides a composition for forming an antireflection film, which is used for an antireflection film for lithography, and when the irradiation light of a KrF excimer laser, an ArF excimer laser, or an F2 excimer laser is used for microfabrication, This anti-reflective film for photolithography absorbs reflected light from the substrate effectively, does not mix with the photoresist layer, and can be quickly removed in the subsequent removal process. Compared with photoresist, it has more Great dry etch speed. The present invention also provides a method for forming an antireflection film for lithography and a method for forming a photoresist pattern using the composition for forming an antireflection film.

disclosure of invention

The present invention, as a first aspect, is a composition for forming an antireflection film, characterized in that it contains a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, a compound having a hydroxyalkyl structure as a nitrogen atom A triazinetrione oligomer compound with a substituent on the nitrogen atom or a triazinetrione macromolecular compound having a hydroxyalkyl structure as a substituent on the nitrogen atom;

As a second viewpoint, the composition for forming an antireflection film as described in the first viewpoint, wherein the above-mentioned triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom is a compound represented by formula (1) (formula Among them, A ₁ , A ₂ and A ₃ represent hydrogen atom, methyl or ethyl group respectively, X represents -OC(=O)-, -S-, -O- or -NR-, where R represents hydrogen atom or methyl group , M represents an alkyl group with 1 to 6 carbons, phenyl, naphthyl, halogen atom, alkoxycarbonyl with 1 to 6 carbons, nitro, cyano, alkane with 1 to 6 carbons phenyl ring, naphthalene ring or anthracene ring substituted by an oxy group or an alkylthio group with 1 to 6 carbons);

As a third viewpoint, the composition for forming an antireflection film as described in the first viewpoint, wherein the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, The triazinetriketone oligomer compound of the substituent or the triazinetriketone macromolecular compound having a hydroxyalkyl structure as the substituent on the nitrogen atom are, have the substituent shown in formula (2) or formula (3) as The triazinetrione compound of the substituent on the nitrogen atom, or the triazinetrione compound having the structure that at least two triazinetrione rings are connected by the linking group shown in formula (4) or formula (5) on its nitrogen atom A ketone oligomer compound or a triazine triketone macromolecular compound (wherein A ₁ , A ₂ and A ₃ are the same as defined above, Y represents a direct bond or -C(=O)-, Ar represents that the carbon number can be 1 Alkyl with 6 to 6, phenyl, naphthyl, halogen atom, alkoxycarbonyl with 1 to 6 carbons, nitro, carboxyl, cyano, alkoxy with 1 to 6 carbons, hydroxyl, thiol group, an alkylthio group with 1 to 6 carbons or a benzene or naphthalene ring substituted by an amino group, Q represents an alkyl group with 1 to 6 carbons, a cycloalkyl group with 5 to 8 carbons, Ar or -CH ₂ -Ar-CH ₂ -, R ₁ represents an alkyl group with 1 to 6 carbons, phenyl or benzyl, R ₂ represents a hydrogen atom, an alkyl group with 1 to 6 carbons, phenyl or benzyl);

As a 4th viewpoint, it is the composition for forming an antireflection film as described in the 3rd viewpoint, wherein the above-mentioned triazinetrione compound having a substituent represented by formula (2) or formula (3) has formula (6) or formula (7) Compounds with the structure shown (in the formula, A ₁ , A ₂ , A ₃ , Y, Ar, R ₁ and R ₂ are the same as defined above);

As a 5th viewpoint, it is the composition for forming an antireflection film as described in the 3rd viewpoint, wherein the linking group having at least two triazinetrione rings on its nitrogen atom is represented by formula (4) or formula (5) The triazinetrione oligomer compound or triazinetrione macromolecular compound of the connected structure is a compound having a structure shown in formula (8) or formula (9) (wherein A ₁ , A ₂ , A ₃ , Y, Ar, _Q , R and R are the _same as defined above);

As a sixth aspect, the composition for forming an antireflection film as described in the first aspect, wherein the above-mentioned triazinetrione oligomer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom or having a hydroxyalkyl structure as a nitrogen atom The triazinetrione macromolecular compound of the substituent on the atom is, the reaction product of the compound shown in formula (10) and the compound shown in formula (11) or formula (12) (wherein R ₃ represents that carbon number is 1 ~6 alkyl, alkenyl, phenyl, benzyl or 2,3-epoxypropyl with 3 to 6 carbons, _R4 and _R5 represent alkyl with 1 to 6 carbons, carbon number 3-6 alkenyl, phenyl or benzyl, _R6 represents an alkyl group with 1-6 carbons, phenyl, benzyl or -(CH ₂ ) _n COOH, n represents 1, 2 or 3) ;

As a seventh aspect, the composition for forming an antireflection film as described in the third aspect is characterized in that the above-mentioned triazinetrione compound having a substituent represented by formula (2) as a substituent on the nitrogen atom or having The triazinetrione oligomer compound or the triazinetrione macromolecular compound of the structure that at least two triazinetrione rings are connected by the linking group shown in formula (4) on its nitrogen atom is, by at least two The triazinetriketone compound of the nitrogen atom having the substituent shown in formula (13) on the nitrogen atom and the phenyl group having at least two identical or different substituents selected from carboxyl and hydroxyl shown in formula (14) Compounds produced from compounds or naphthalene compounds (A ₁ , A ₂ , A ₃ , Y and Ar in formulas (13), (14) are the same as defined above);

HO-Y-Ar-Y-OH (14)

The eighth viewpoint is the composition for forming an antireflection film according to the seventh viewpoint, wherein the above-mentioned triazinetrione compound having at least two nitrogen atoms having a substituent represented by formula (13) on the nitrogen atom is, A triazinetrione compound represented by formula (15) (wherein A ₁ , A ₂ , and A ₃ are the same as defined above);

As a ninth aspect, the composition for forming an antireflection film as described in the seventh aspect, wherein the phenyl compound or naphthalene compound of the above-mentioned formula (14) is selected from the compounds represented by the formulas (16) to (21) At least one compound (wherein B represents a hydrogen atom, an alkyl group with a carbon number of 1 to 6, a phenyl group, a naphthyl group, a halogen atom, an alkoxycarbonyl group with a carbon number of 1 to 6, a nitro group, a carboxyl group, a cyano group, etc. group, an alkoxy group with 1 to 6 carbons, a hydroxyl group, a thiol group, an alkylthio group or an amino group with a carbon number of 1 to 6, n represents a number from 1 to 6, m represents a number from 1 to 4, and When n and m are numbers greater than or equal to 2, B can be the same or different);

As a tenth aspect, the composition for forming an antireflection film according to any one of the first to ninth viewpoints further contains a crosslinking agent having at least two crosslinking substituents;

As an eleventh aspect, the composition for forming an antireflection film according to any one of the first to tenth viewpoints further contains an acid and/or an acid generator;

As a twelfth aspect, the composition for forming an antireflection film according to any one of the first to eleventh aspects further contains a substituent having at least one crosslinking group selected from hydroxyl, carboxyl, amino and thiol groups the resin;

A thirteenth aspect is an antireflection film formed by applying the composition for forming an antireflection film according to any one of the first to twelfth aspects on a semiconductor substrate, followed by firing to form an antireflection film. , the attenuation coefficient k value of the antireflection film for light with a wavelength of 248nm is 0.40 to 0.65;

As a 14th viewpoint, it is an antireflection film formed by applying the composition for forming an antireflection film according to any one of the 1st to 12th viewpoints on a semiconductor substrate, and firing to form an antireflection film. , the attenuation coefficient k value of the antireflection film for light with a wavelength of 157nm is 0.20 to 0.50;

As a fifteenth viewpoint, it is an antireflection film formed by applying the antireflection film-forming composition according to any one of the first to twelfth viewpoints on a semiconductor substrate, followed by firing to form an antireflection film , the attenuation coefficient k value of the antireflection film for light with a wavelength of 193nm is 0.20 to 0.60;

As a sixteenth viewpoint, it is a method of forming an antireflection film used in the manufacture of a semiconductor device, by applying the composition for forming an antireflection film according to any one of the first to twelfth viewpoints on a substrate, obtained by firing;

As a 17th viewpoint, it is a method of forming an antireflection film used in the manufacture of a semiconductor device using light with a wavelength of 248nm, a wavelength of 193nm, or a wavelength of 157nm, by applying any one of the first to twelfth viewpoints A composition for forming an anti-reflection film is coated on a substrate and fired to obtain it;

An eighteenth viewpoint is a method for forming a photoresist pattern used in the manufacture of a semiconductor device, comprising the step of: preparing the composition for forming an antireflection film according to any one of the first to twelfth viewpoints The process of forming an anti-reflection film by applying it on the substrate and firing it; the process of forming a photoresist layer on the anti-reflection film; The process of exposing; the process of developing the photoresist layer after exposure.

The nineteenth aspect is the method for forming a photoresist pattern according to the eighteenth aspect, wherein the exposure is performed with light having a wavelength of 248 nm, 193 nm, or 157 nm.

The best way to practice the invention

The present invention relates to a composition for forming an antireflection film, which is characterized in that it contains a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom A triazinetrione oligomer compound or a triazinetrione polymer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, in addition, relates to a composition for forming an antireflection film, which can be used for using a short wavelength Photolithography process for semiconductor device manufacturing by irradiation light, especially KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) or F2 excimer laser (wavelength 157nm).

The composition for forming an antireflective film of the present invention basically comprises a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom The composition of an oligomer compound or a triazinetrione polymer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, and a solvent contains a crosslinking catalyst, a surfactant, and the like as optional components. The solid content of the antireflection film-forming composition of the present invention is, for example, 0.1 to 50% by mass, or, for example, 0.5 to 30% by mass. The term "solid content" herein refers to a component in which a solvent component is removed from the composition for forming an antireflection film.

In addition, in the composition for forming an antireflection film of the present invention, as a triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, a triazine having a hydroxyalkyl structure as a substituent on a nitrogen atom The blending amount of a triketone oligomer compound or a triazinetrione polymer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom is 10% by mass or more per 100% by mass of the total solid content, for example 30% by mass to 99% by mass, for example, 50% by mass to 99% by mass, further, for example, 60% by mass to 95% by mass.

In the antireflection film-forming composition of the present invention, examples of the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom include compounds represented by formula (1). In formula (1), A ₁ , A ₂ and A ₃ represent hydrogen atom, methyl or ethyl group respectively, X represents -OC(=O)-, -S-, -O- or -NR-, where R represents A hydrogen atom or a methyl group, M means that it can be replaced by an alkyl group with 1 to 6 carbons, phenyl, naphthyl, halogen atom, alkoxycarbonyl with 1 to 6 carbons, nitro, cyano, or A benzene ring, naphthalene ring or anthracene ring substituted by an alkoxy group of 1 to 6 or an alkylthio group with a carbon number of 1 to 6.

Such a compound of formula (1), for example, can be obtained by reacting a compound shown in formula (15) with a compound shown in formula (22) (in formula (22), X represents -OC(=O)-, -S-, -O- or -NR-, where R represents a hydrogen atom or a methyl group, and M represents an alkyl, phenyl, naphthyl, halogen atom with a carbon number of 1 to 6 that can be replaced by a carbon number of 1 to 6 alkoxycarbonyl, nitro, cyano, alkoxy with 1 to 6 carbons or alkylthio with 1 to 6 carbons substituted benzene ring, naphthalene ring or anthracycline).

The reaction of the compound shown in such formula (15) and the compound shown in formula (22) is preferably dissolved in benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether It is carried out in the solution state of organic solvents such as acetate and N-methylpyrrolidone. In this reaction, the compound of formula (15) and the compound of formula (22) may be used alone or in combination of two or more compounds. In addition, in this reaction, quaternary ammonium salts such as benzyltriethylammonium chloride, tetrabutylammonium chloride, and tetraethylammonium bromide can be used as a catalyst for this reaction. The reaction temperature and reaction time of this reaction depend on the compound used, concentration, etc., and the reaction time can be appropriately selected from the range of 0.1 to 100 hours, and the reaction temperature can be appropriately selected from the range of 20°C to 200°C. When using a catalyst, it can use it in the range of 0.001-50 mass % with respect to the whole mass of the compound used.

In the anti-reflection film-forming composition of the present invention containing the compound represented by formula (1), the characteristics of the anti-reflection film formed by the anti-reflection film-forming composition, especially for the photolithographic process used The light absorption characteristics, attenuation coefficient, refractive index, etc. of the irradiated light largely depend on the type of compound of formula (22) used in this reaction. In addition, the type of the compound of formula (22) used also affects the time required for the removal step by etching of the antireflection film formed from the antireflection film forming composition of the present invention. In particular, the type and number of substituents of benzene ring, naphthalene ring or anthracene ring in the compound of formula (22) have an impact on the time required for the removal process of the anti-reflection film by etching. Substituents of heteroatoms such as atoms, oxygen atoms, and sulfur atoms, or increasing the number of such substituents can shorten the time required for the removal process by etching.

When the composition for forming an anti-reflection film of the present invention containing a compound represented by formula (1) is applied to a process using light with a wavelength of 248nm (KrF excimer laser), it is preferable to use a compound of formula (22) having A compound of a naphthalene ring or an anthracycline (M is a naphthalene ring or an anthracene ring). In addition, when applied to a process using light with a wavelength of 193 nm (ArF excimer laser) and 157 nm (F2 excimer laser), it is preferable to use a compound having a benzene ring (M is a benzene ring).

As the compound of formula (15) used in the reaction for obtaining the compound of formula (1), for example, tris-(2,3-epoxypropyl)-isocyanurate, tris-(2-methyl - 2,3-epoxypropyl)-isocyanurate, tris-(2,3-epoxybutyl)-isocyanurate, and the like.

As the compound of formula (22) used in the reaction for obtaining the compound of formula (1), for example, benzoic acid, monoethyl isophthalate, 2,4-dibromobenzoic acid, 4-methyl Benzoic acid, 2-methoxybenzoic acid, 2,3,5-triiodobenzoic acid, 2-chloro-4-nitrobenzoic acid, 4-fluorobenzoic acid, 4-iodobenzoic acid, 4-bromobenzoic acid , 4-tert-butylbenzoic acid, 3-trifluoromethylbenzoic acid, 2-nitrobenzoic acid, 4-isopropoxybenzoic acid, 3-cyanobenzoic acid, 3-phenylbenzoic acid, 3- Bromo-4-methylbenzoic acid, 2,4,6-tribromobenzoic acid, 4-methylthiobenzoic acid, 2-bromo-4-fluorobenzoic acid, etc.

In addition, as the compound of formula (22), for example, naphthalene-2-carboxylic acid, 1-bromonaphthalene-2-carboxylic acid, 4-bromo-3-methoxy-naphthalene-2-carboxylic acid, 3-methylnaphthalene -2-carboxylic acid, 4-fluoronaphthalene-1-carboxylic acid, 4-nitronaphthalene-1-carboxylic acid, 5-bromonaphthalene-1-carboxylic acid, 8-iodonaphthalene-1-carboxylic acid, anthracene-9-carboxylic acid, anthracene- 2-Formic acid, 10-bromoanthracene-9-carboxylic acid, etc.

In addition, as the compound of formula (22), for example, phenol, 4-methylphenol, 4-chlorophenol, 4-bromophenol, 4-nitrophenol, 2,3,4,5-tetrabromophenol, Pentabromophenol, 4-bromo-2-fluorophenol, 4-iodophenol, 2,4,6-triiodophenol, 2,5-dimethyl-4-iodophenol, 4-methylthiophenol, 3- Methoxyphenol, 3-bromophenol, 2-cyanophenol, 2,6-diiodo-4-cyanophenol, methyl 3-hydroxybenzoate, 2-naphthol, 1-bromo-2-naphthol , 2-nitro-1-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 2,4-dichloro-1-naphthol, 2-hydroxynaphthalene-3 -Methyl formate, 2-hydroxyanthracene, 9-hydroxyanthracene, etc.

In addition, as the compound of formula (22), for example, aniline, 3-chloroaniline, 2-bromoaniline, 4-iodoaniline, 3-methoxyaniline, 3-methylthioaniline, 4-nitroaniline , 3-isopropylaniline, 3,5-dibromoaniline, 2-fluoro-4-iodoaniline, 2-amino-5-iodobenzoic acid methyl ester, 2,4,6-tribromoaniline, 4-bromoaniline -3-methylaniline, 2-bromo-4-nitroaniline, 2-bromo-5-trifluoromethylaniline, 3-phenylaniline, 1-aminonaphthalene, 1-amino-4-bromonaphthalene, 1 -Amino-2-nitronaphthalene, 1-aminoanthracene, 9-aminoanthracene, etc.

Further, as the compound of formula (22), for example, thiophenol, 2-methylthiophenol, 4-chlorothiophenol, pentachlorothiophenol, 3-methoxythiophenol 3-bromo Thiophenol, methyl 2-mercaptobenzoate, 4-nitrothiophenol, 3-iodothiophenol, 1-thionaphthol, 9-mercaptoanthracene, etc.

In addition, as the compound reacting with the compound of formula (8), in addition to the compound of formula (15), for example, thiophene-2-carboxylic acid, 5-bromothiophene-2-carboxylic acid, phenylacetic acid, 4-bromobenzene Oxyacetic acid, benzyl alcohol, 2,4-dibromobenzyl alcohol, 3-bromocinnamic acid, 9-hydroxymethylanthracene, thiazole-2-carboxylic acid, 2-amino-5-bromothiazole, etc. compound of.

As the compound of formula (1) contained in the composition for forming an antireflection film of the present invention, for example, the following formula (23) (compound No. 1 in the following Table 1), the following formula (24) (following Compound No. 15) in Table 1.

Similarly, compounds shown in Table 1 (in the table, Ph represents phenyl, 1-Nap represents 1-naphthyl, 2-Nap represents 2-naphthyl, and 9-Ant represents 9-anthracenyl) can also be cited.

Table 1

In the antireflection film-forming composition of the present invention, the compound represented by formula (1) may be used alone or in combination of two or more. The compounding amount of such a compound of formula (1) is 10% by mass or more in the total solid content, for example, 30% by mass to 99% by mass, for example, 50% by mass to 99% by mass, further, for example, 60% by mass Mass ~ 95% mass.

In the composition for forming an antireflection film of the present invention, as the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, compounds represented by formula (2) or formula (3) can also be enumerated. The substituent is a triazinetrione compound as a substituent on a nitrogen atom, a triazinetrione ring having a structure in which at least two triazinetrione rings are connected by a linking group shown in formula (4) or formula (5) on its nitrogen atom An azinetrione oligomer compound or a triazinetrione polymer compound. In the formulas (2), (3), (4), and (5), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group, respectively, and Y represents a direct bond or -C(=O)- , Ar represents an alkyl group, phenyl group, naphthyl group, halogen atom, alkoxycarbonyl group, nitro group, carboxyl group, cyano group, carbon number of 1 to 6 that can be replaced by a carbon number of 1 to 6 alkoxy, hydroxyl, thiol, alkylthio with 1 to 6 carbons, or benzene or naphthalene ring substituted by amino, Q represents an alkyl group with 1 to 6 carbons, and 5 to 8 carbons Cycloalkyl, Ar or -CH ₂ -Ar-CH ₂ -, R ₁ represents an alkyl group with 1 to 6 carbons, phenyl or benzyl, R ₂ represents a hydrogen atom, an alkane with 1 to 6 carbons base, phenyl or benzyl.

As the above-mentioned triazinetrione compound having a substituent represented by formula (2) as a substituent on the nitrogen atom, a compound having a structure represented by formula (6) can be used. In formula (6), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group respectively, Y represents a direct bond or -C(=O)-, and Ar represents an alkane with a carbon number of 1 to 6 radical, phenyl, naphthyl, halogen atom, alkoxycarbonyl with 1 to 6 carbons, nitro, carboxyl, cyano, alkoxy with 1 to 6 carbons, hydroxyl, thiol, carbon 1-6 alkylthio or amino-substituted benzene or naphthalene rings.

The compound of formula (6) can have formula (13) on nitrogen atom

HO-Y-Ar-Y-OH (14)

(In the formula, A ₁ , A ₂ and A ₃ respectively represent a hydrogen atom, a methyl group or an ethyl group) The triazinetrione compound of the substituent shown in the formula (14) (In the formula, Y represents a direct bond or -C (=O)-, Ar represents an alkyl group, phenyl group, naphthyl group, halogen atom, alkoxycarbonyl group, nitro group, carboxyl group, cyano group, carbon group with a carbon number of 1 to 6, a carbon number of 1 to 6 It can be obtained by reacting a phenyl compound or a naphthalene compound represented by an alkoxy group with 1 to 6, a hydroxyl group, a thiol group, an alkylthio group with a carbon number of 1 to 6, or an amino-substituted benzene ring or naphthalene ring). In this reaction, only one kind of compound represented by formula (14) may be used, and two or more kinds of compounds may be used in combination. This reaction is preferably carried out in a solution state dissolved in an organic solvent such as benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, or the like. In addition, quaternary ammonium salts such as benzyltriethylammonium chloride, tetrabutylammonium chloride, and tetraethylammonium bromide can also be used as a catalyst for this reaction. The reaction temperature and reaction time of this reaction depend on the compound used, concentration, etc., and the reaction time can be appropriately selected from the range of 0.1 to 100 hours, and the reaction temperature can be appropriately selected from the range of 20°C to 200°C. When a catalyst is used, the catalyst can be used in an amount of 0.001 to 50% by mass relative to the total mass of the compound used.

As a triazinetrione compound having a substituent represented by formula (13) on the nitrogen atom, it can be known that there are one, two or three nitrogen atoms having a substituent of formula (13) on the nitrogen atom, However, any one of them may be used in the present invention, or they may be used in combination. It is preferable to use a compound having three substituents of formula (13), that is, a compound represented by formula (15). In formula (15), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group respectively, preferably use a compound in which A ₁ , A ₂ and A ₃ are a hydrogen atom, and A ₁ and A ₃ are a hydrogen atom, A ₂ is a methyl compound.

In this reaction, when using a triazinetrione compound having two or three nitrogen atoms having substituents of formula (13), it is known that there are cases where all substituents react with compounds of formula (14) and only Where one or both of the substituents react with the compound of formula (14), the triazinetrione compound used in the antireflection film-forming composition of the present invention includes any of them. In the antireflection film forming composition of the present invention, it is preferred to use the compound obtained by reacting all the substituents of the compound formula (15) having three substituents of the formula (13) with the compound of the formula (14). Compounds shown in formula (25) (in formula (25), Y represents a direct bond or -C(=O)-, Ar represents an alkyl, phenyl, naphthyl, halogen atom that can be replaced by a carbon number of 1 to 6 , alkoxycarbonyl with 1 to 6 carbons, nitro, carboxyl, cyano, alkoxy with 1 to 6 carbons, hydroxyl, thiol, alkylthio with 1 to 6 carbons or amino-substituted benzene ring or naphthalene ring).

Examples of the compound of formula (14) used in the reaction with the triazinetrione compound having a substituent represented by formula (13) on the nitrogen atom include compounds represented by formulas (16) to (21)

(B in the formula represents a hydrogen atom, an alkyl group with 1 to 6 carbons, phenyl, naphthyl, a halogen atom, an alkoxycarbonyl group with 1 to 6 carbons, a nitro group, a carboxyl group, a cyano group, and a carbon number of 1 to 6 1 to 6 alkoxy, hydroxyl, thiol, alkylthio or amino with 1 to 6 carbons, n represents the number of 1 to 6, m represents the number of 1 to 4, and where n and m are When the number is greater than or equal to 2, B may be the same or different). In this reaction, the compounds of the formulas (16) to (21) may be used alone or in combination of two or more.

As the triazinetrione compound having a substituent represented by formula (3) as a substituent on the nitrogen atom, a compound having a structure represented by formula (7) can be used. In the formula (7), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group respectively, R ₁ represents an alkyl group with 1 to 6 carbon atoms, a phenyl group or a benzyl group, R ₂ represents a hydrogen atom, An alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-pentyl group, isopropyl group, cyclohexyl group and the like.

The compound of formula (7) can be converted into dioxolanone (dioxiranone) by making carbon dioxide react with a triazinetrione compound having a substituent shown in formula (13) on the nitrogen atom. ) ring, it is produced by reacting with the amine compound formula (26).

The reaction of converting the epoxy ring moiety into a dioxolanone ring can be carried out, for example, by reacting it with carbon dioxide in the presence of lithium bromide. In addition, the reaction between the dioxolanone ring and the amine compound formula (26) can be carried out, for example, by reacting in N,N-dimethylformamide at 70°C for 48 hours.

In this reaction, when using a triazinetrione compound having two or three nitrogen atoms having substituents of the formula (13), it can be seen that all of the epoxy rings are converted into dioxolanone (dioxiranone) ) ring, converted into the situation of the substituent of formula (3), and only one or two of the epoxy ring parts are converted into the situation of the substituent of formula (3), and the combination of forming anti-reflection film of the present invention The triazinetrione compound used in the compound is a compound including any of them.

As the triazinetrione compound having a substituent represented by the formula (13) on the nitrogen atom, a compound having three substituents represented by the formula (13), that is, a compound of the above-mentioned formula (15) is preferably used. Thereby, in the composition that forms antireflection film of the present invention, preferably use the compound that all epoxy rings of the compound formula (15) that has three substituting groups of formula (13) are converted into the substituting group of formula (3) , that is, the compound represented by formula (27) is preferably used (in formula (27), R ₁ and R ₂ are the same as defined above).

As the compound of formula (26) used in the reaction with the triazinetrione compound having a substituent represented by formula (13) on the nitrogen atom, for example, methylamine, ethylamine, isopropylamine, n- Butylamine, cyclohexylamine, aniline, benzylamine, dimethylamine, diethylamine, diisopropylamine, dibenzylamine, diphenylamine, etc. In this reaction, the compound of formula (26) may be used alone or in combination of two or more.

In the antireflection forming composition of the present invention, the compound represented by formula (27) may be used alone or in combination of two or more. The compounding quantity of such a compound of formula (27) is 10 mass % or more in total solid content, for example, it is 30 mass % - 99 mass %, for example, it is 50 mass % - 99 mass %, for example, it is 60 mass % ~95% mass.

In the antireflection film-forming composition of the present invention containing the compound represented by formula (27), the characteristics of the antireflection film formed by the antireflection film-forming composition, especially for the photolithographic process used The light absorption characteristics, attenuation coefficient, and refractive index of the irradiated light are characteristics that also depend on the type of compound of formula (26) used in this reaction.

In the composition for forming an antireflective film of the present invention, the triazinetrione oligomerization of the above-mentioned structure having at least two triazinetrione ring structures connected by the linking group represented by the formula (4) through its nitrogen atom As a compound compound or a triazinetrione polymer compound, a triazinetrione oligomer compound or a triazinetrione polymer compound having a structure represented by formula (8) can be used. In the formula (8), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group respectively, Y represents a direct bond or -C(=O)-, Ar represents an alkane with a carbon number of 1 to 6 radical, phenyl, naphthyl, halogen atom, alkoxycarbonyl with 1 to 6 carbons, nitro, carboxyl, cyano, alkoxy with 1 to 6 carbons, hydroxyl, thiol, carbon 1-6 alkylthio or amino-substituted benzene or naphthalene rings.

The molecular weight of the triazinetrione oligomer compound and the triazinetrione polymer compound having a structure represented by formula (8) in the antireflection film-forming composition of the present invention is not particularly limited, but The average molecular weight is, for example, 700 to 200,000, for example, 1,000 to 50,000.

Have the triazine triketone oligomer compound of the structure shown in formula (8), triazine triketone macromolecule compound, can have the substituting shown in above-mentioned formula (13) on the nitrogen atom by making two or three It can be obtained by reacting a triazinetrione compound having a nitrogen atom in the group with an aromatic compound represented by the above-mentioned formula (14). In this reaction, only one compound represented by the above formula (14) may be used, or two or more compounds may be used in combination.

This reaction is preferably carried out in a solution state dissolved in an organic solvent such as benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, or the like. In addition, quaternary ammonium salts such as benzyltriethylammonium chloride, tetrabutylammonium chloride, and tetraethylammonium bromide can also be used as a catalyst for this reaction. The reaction temperature and reaction time of this reaction depend on the compound used, concentration, etc., and the reaction time can be appropriately selected from the range of 0.1 to 100 hours, and the reaction temperature can be appropriately selected from the range of 20°C to 200°C. When using a catalyst, it can use it in the range of 0.001-50 mass % with respect to the whole mass of the compound used.

In this reaction, a triazinetrione compound having two or three nitrogen atoms having a substituent represented by the above formula (13) on the nitrogen atom may be used alone or in combination. A compound having three substituents of formula (13), ie, a compound represented by formula (15) above is preferably used.

In this reaction, it can be known that there are two cases in which all the substituents of the triazinetrione compound having two or three nitrogen atoms having substituents of formula (13) react with the compound of formula (14) , participate in the formation of the linking group of the above formula (4); and one or two substituents of the formula (13) participate in the formation of the linking group of (4), and the remaining substituents of the formula (13) are unreacted or participate in The case of formation of the substituent of formula (2). Among the triazinetrione oligomer compounds and triazinetrione polymer compounds obtained by this reaction, it can be seen that there are two cases as follows, that is, one or both of the triazinetrione compounds used as the raw materials for their production The substituent of (13) participates in the formation of the connecting group of formula (4), that is, participates in the formation of oligomer structure and polymer structure, and the substituents of the remaining formula (13) are unreacted or participate in the substituent of formula (2) The formation of the situation; all (that is, two or three) substituents of formula (13) participate in the formation of the linking group of formula (4), that is, participate in the formation of oligomer structure and macromolecular structure.

In the manufacture of the triazinetrione oligomer compound and the triazinetrione polymer compound carried out by this reaction, it is preferable to use the compound of the above-mentioned formula (15) as a compound having three substituents of the formula (13), It is particularly preferable to use a compound of formula (28) (wherein A ₄ represents a hydrogen atom or a methyl group).

As the compound of the formula (14) used in the manufacture of the triazinetrione oligomer compound and the triazinetrione polymer compound having the structure shown in the formula (8), the above-mentioned formulas (16) to (21 ) represented by a compound having a naphthalene ring or a compound having a benzene ring. These compounds may be used alone or in combination of two or more.

The anti-reflection film composition of the present invention contains the triazinetrione compound having a substituent represented by the formula (13) on the nitrogen atom and a benzene compound or a naphthalene compound represented by the formula (14). An antireflection film composition of a triazinetrione compound, a triazinetrione oligomer compound, and a triazinetrione polymer compound. In the antireflection film composition of the present invention, any one of the following compositions is also included: a composition containing only such a triazinetrione compound, a composition containing only a triazinetrione oligomer compound, a composition containing only a triazinetrione oligomer compound, Compositions containing triazinetrione macromolecular compounds, in addition, also include any of the following compositions: compositions comprising such a mixture of triazinetrione compounds and triazinetrione oligomer compounds, comprising such A composition comprising a mixture of a triazinetrione compound and a triazinetrione polymer compound, a composition comprising a mixture of such a triazinetrione oligomer compound and a triazinetrione polymer compound, comprising such a triazine Composition of a mixture of a triketone compound, a triazinetrione oligomer compound, and a triazinetrione polymer compound.

A triazinetrione compound obtained by reacting a triazinetrione compound having a substituent represented by formula (13) on a nitrogen atom with a compound of formula (14), or a triazinetrione oligomer compound , or triazinetrione macromolecular compound in the composition for forming an antireflection film of the present invention, the characteristics of the antireflection film formed by the composition, especially the light absorption characteristics for the irradiating light used in the photolithography process, The attenuation coefficient, the refractive index, and the like are properties greatly dependent on the type of compound of formula (14) used in this reaction. In addition, the type of the compound of formula (14) used also affects the time required for the removal step by etching of the antireflection film formed from the antireflection film forming composition of the present invention. In particular, the type and number of substituents of the benzene ring and the naphthalene ring in the compound of formula (14) have an influence on the time required for the removal process of the antireflection film by etching. Substituents of heteroatoms such as atoms and sulfur atoms or increasing the number of such substituents can shorten the time required for the removal step by etching.

When the antireflection film composition of the present invention is used for the process of using the light of wavelength 248nm (KrF excimer laser), as the compound of formula (14), it is preferable to use Compounds of naphthalene rings. In addition, when used in a process using light with a wavelength of 193 nm (ArF excimer laser) and a wavelength of 157 nm (F2 excimer laser), it is preferable to use compounds having benzene rings represented by formulas (19) to (21).

Examples of such compounds having a naphthalene ring include 3-hydroxynaphthalene-2-carboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 1,6-dibromo-2- Hydroxynaphthalene-3-carboxylic acid, 6-hydroxynaphthalene-2-carboxylic acid, 3,7-dihydroxynaphthalene-2-carboxylic acid, 4-hydroxy-1-phenyl-naphthalene-2-carboxylic acid, 6-hydroxynaphthalene-2- Formic acid, 4-bromonaphthalene-1,8-dicarboxylic acid, 2-hydroxynaphthalene-1-carboxylic acid, 4-bromonaphthalene-1,4-dicarboxylic acid, 1,5-dihydroxynaphthalene, 2,6-dibromo- 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 6-ethoxy-2,3-dihydroxynaphthalene, etc.

As such a compound having a benzene ring, for example, 3-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-amino-3-hydroxybenzoic acid, 2,5-dichloro-3-hydroxy- 6-methoxybenzoic acid, 2,4,6-triiodo-3-hydroxybenzoic acid, 2,4,6-tribromo-3-hydroxybenzoic acid, 2-bromo-4,6-dimethyl- 3-Hydroxybenzoic acid, 2-fluoro-5-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dibromo-4-hydroxybenzoic acid, 2,4-dihydroxy-5- Bromobenzoic acid, 3-iodo-5-nitro-4-hydroxybenzoic acid, 2-hydroxybenzoic acid, 4-chloro-2-hydroxybenzoic acid, 3,5-diiodo-2-hydroxybenzoic acid, 3- Methoxy-2-hydroxybenzoic acid, 2-hydroxy-6-isopropyl-3-methylbenzoic acid, 4-amino-3,5-diiodo-2-hydroxybenzoic acid, 4,5-dichloro -Benzene-1,3-dicarboxylic acid, 5-amino-2,4,6-triiodo-isophthalic acid, benzene-1,4-dicarboxylic acid, 2,3,5,6-tetrabromo-benzene- 1,4-dicarboxylic acid, 4,5-dichlorophthalic acid, 5-methoxy-3-methyl-phthalic acid, 3,4,5,6-tetrabromophthalic acid, etc.

In the composition for forming an antireflection film of the present invention, as the above-mentioned triazinetrione oligomer having a structure in which at least two triazinetrione rings are linked by a linking group represented by formula (5) at its nitrogen atom As the compound or the triazinetrione polymer compound, a triazinetrione oligomer compound or a triazinetrione polymer compound having a structure represented by the formula (9) can be used. In formula (9), A ₁ , A ₂ and A ₃ represent a hydrogen atom, a methyl group or an ethyl group, respectively, and Q represents an alkyl group with 1 to 6 carbons, a cycloalkyl group with 5 to 8 carbons, Ar or -CH ₂ -Ar-CH ₂ -, R ₁ represents an alkyl, phenyl or benzyl group with 1 to 6 carbons, R ₂ represents a hydrogen atom, an alkyl group with 1 to 6 carbons, phenyl or benzyl .

The molecular weight of the triazinetrione oligomer compound and the triazinetrione polymer compound having a structure represented by formula (9) in the composition for forming an antireflection film of the present invention is not particularly limited, but as a weight The average molecular weight is, for example, 700 to 200,000, for example, 1,000 to 50,000.

Have the triazine triketone oligomer compound of the structure shown in formula (9), triazine triketone macromolecular compound, can by making carbon dioxide and the triazine triketone triketone that has the substituting group shown in formula (13) on nitrogen atom The ketone compound is reacted to convert the epoxy ring part into a dioxolanone (dioxilanone) ring, and then react with the amine compound formula (29) to produce it.

The reaction between the dioxolanone ring and the amine compound formula (29) can be carried out, for example, by reacting in N,N-dimethylformamide solvent at 70°C for 48 hours. In this reaction, only one kind of compound represented by formula (29) may be used, and two or more kinds thereof may be used in combination.

In this reaction, a triazinetrione compound having two or three nitrogen atoms having a substituent represented by formula (13) on the nitrogen atom may be used alone or in combination. A compound having three substituents of formula (13), ie, a compound represented by formula (15) above is preferably used.

In this reaction, it is known that there are two cases where all the epoxy ring moieties of the triazinetrione compound having two or three nitrogen atoms having substituents of the formula (13) are transformed into dioxa After the cyclopentanone (Giokisilanon) ring, reacts with the compound of formula (29) to participate in the formation of the linking group of the above formula (5); and one or two epoxy rings of the formula (13) partly participate in (5) The formation of the connecting group, the remaining substituents of formula (13) are unreacted or participate in the formation of substituents of formula (3) (R ₂ is a hydrogen atom). In the triazinetrione oligomer compound and triazinetrione macromolecular compound obtained by this reaction, it can be known that there are the following two cases, that is, one or two of the triazine compounds used as the raw materials for their production are of the formula (13 ) substituent participates in the formation of the linking group of formula (5), that is, participates in the formation of oligomer structure and polymer structure, and the remaining substituents of formula (13) are unreacted or participate in the formation of substituents of formula (3); or All (that is, two or three) substituents of formula (13) participate in the formation of the linking group of formula (5), that is, participate in the formation of oligomer structure and polymer structure.

In the manufacture of triazinetrione oligomer compounds and triazinetrione polymer compounds utilizing this reaction, it is preferred to use the compound of the above formula (15) as a compound having three substituents of formula (13), particularly preferably The compound of formula (28) above is used.

As the compound of the formula (29) used in the manufacture of the triazinetrione oligomer compound and the triazinetrione polymer compound having the structure represented by the formula (9), for example, ethylenediamine, propylenediamine, Amine, phenylenediamine, 2-hydroxy-1,3-propanediamine, 1,4-cyclohexanediamine, phenylenedimethyldiamine, 2,6-dichlorophenylenediamine, 1,4-di Aminonaphthalene, 1,5-diaminonaphthalene, etc. These compounds may be used alone or in combination of two or more.

In the composition for forming an antireflection film of the present invention containing a triazinetrione oligomer compound and a triazinetrione polymer compound having a structure represented by formula (9), the antireflection film formed by the composition The properties, particularly the light absorption properties, attenuation coefficient, refractive index and the like with respect to the irradiating light used in the photolithography process are properties depending on the kind of the compound of the formula (29) used in this reaction. In addition, the type of the compound of formula (29) used also affects the time required for the removal step by etching of the antireflection film formed from the antireflection film forming composition of the present invention.

When the antireflection film composition of the present invention is used in the process of using light with a wavelength of 248nm (KrF excimer laser), as the compound of formula (29), it is preferable to use 1,4-diaminonaphthalene, 1,5- Compounds having a naphthalene ring such as diaminonaphthalene and 2,3-diaminonaphthalene. In addition, when used in a process using light with a wavelength of 193nm (ArF excimer laser) and a wavelength of 157nm (F2 excimer laser), it is preferable to use phenylenediamine, xylylenediamine, and 2,6-dichlorophenylenediamine. , 3,5-dibromo-1,2-phenylenediamine, 3,4,5,6-tetraiodo-1,2-phenylenediamine and other compounds having a benzene ring.

As a triazinetrione compound having a substituent represented by formula (2) or formula (3) as a substituent on a nitrogen atom contained in the composition for forming an antireflection film of the present invention, at least two triazine The triazinetrione oligomer compound or the triazinetrione macromolecular compound of the structure that the linking group shown in formula (4) or formula (5) connects by triketone ring on its nitrogen atom, formula (2), The substituents of formula (3) and the linking groups of formulas (4) and (5) are listed below.

For example, as a substituent of formula (2), it is a substituent of formula (30)-(37).

For example, as a substituent of formula (3), it is a substituent of formula (38)-(43).

Moreover, as a linking group of formula (4), it is a linking group of formula (44)-(52), for example.

Moreover, as a linking group of formula (5), it is a linking group of formula (54)-(55), for example.

In the composition for forming an antireflection film of the present invention, as the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, compounds represented by formula (10) and formula (11) can also be enumerated. Or a reaction product of a compound represented by formula (12). R ₃ represents an alkyl group with a carbon number of 1 to 6, an alkenyl group with a carbon number of 3 to 6, a phenyl group, a benzyl group or a 2,3-epoxypropyl group, and R ₄ and R ₅ represent a group with a carbon number of 1 to 6. 6 alkyl, alkenyl, phenyl or benzyl with 3 to 6 carbons, R ₆ represents alkyl, phenyl, benzyl or -(CH ₂ ) _n COOH, n with 1 to 6 carbons Means 1, 2 or 3. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-pentyl group, isopropyl group, cyclohexyl group and the like. Examples of the alkenyl group having 3 to 6 carbon atoms include allyl, 2-butenyl, 3-butenyl, 2-pentenyl and the like.

By making the compounds of formula (10) and formula (11), in solvents such as cyclohexanone, propylene glycol monomethyl ether, etc., using benzyl triethylammonium bromide as a catalyst, react under heating and reflux, as the reaction As a product, a compound composed of a structural unit represented by formula (56) can be obtained.

In addition, when R in formula (10) is ₂ , when 3-epoxypropyl, its three epoxy ring moieties can all react with the compound of formula (11), can obtain the structure shown in formula (57) unit compound.

The amount of structural units of formula (56) and formula (57) contained in the reaction product changes with the reaction conditions. As the reaction product of the composition for forming an antireflection film used in the present invention, it is preferable to use an oligomer compound, a high molecular compound. In addition, it is preferable to use an oligomer compound or a polymer compound containing 1 to 10,000 structural units of the formula (57) and having a molecular weight of 400 to 1,000,000 as a weight average molecular weight.

By making the compounds of formula (10) and formula (12), in solvents such as cyclohexanone, propylene glycol monomethyl ether, etc., using benzyltriethylammonium bromide as a catalyst, reacting under heating and reflux, can obtain reaction product. In formula (12), when _R6 is an alkyl group, phenyl group or benzyl group with 1 to 6 carbon atoms, a carboxyl group of formula (12) reacted with an epoxy ring of formula (10) can be obtained as a reaction product compound of. When R ₆ in formula (12) is -(CH ₂ ) _n COOH, its two carboxyl groups react with the epoxy ring of the compound shown in other formula (10) respectively, as the reaction product can be obtained by the formula (58 ) The compound formed by the structural unit shown in ).

In addition, when _R in formula (10) is 2,3-epoxypropyl, its three epoxy ring parts can all react with the carboxyl group of formula (12), and the structure shown in formula (59) can be obtained unit compound.

The number of structural units of formula (58) and formula (59) contained in the reaction product varies with the reaction conditions. As the reaction product used in the composition for forming an antireflective film of the present invention, it is preferable to use an oligomer compound containing 1 to 10,000 structural units of the formula (58) and having a molecular weight of 400 to 1,000,000 in terms of weight average molecular weight, polymer compound. In addition, it is preferable to use an oligomer compound or a polymer compound containing 1 to 10,000 structural units of the formula (59) and having a molecular weight of 400 to 1,000,000 in terms of weight average molecular weight.

In the antireflection film-forming composition of the present invention, a reaction product containing a structural unit of formula (56) and a reaction product containing a structural unit of formula (58) may be used in combination.

Examples of the compound of formula (10) used in the production of the reaction product include monoallyl diglycidyl isocyanuric acid, monomethyl diglycidyl isocyanuric acid, mono Ethyl diglycidyl isocyanuric acid, monobutyl diglycidyl isocyanuric acid, monophenyl diglycidyl isocyanuric acid, monobenzyl diglycidyl isocyanuric acid .

As the compound of formula (11), for example, monoallyl isocyanuric acid, monomethylisocyanuric acid, monoethylisocyanuric acid, monobutylisocyanuric acid, Monophenyl isocyanuric acid, monobenzyl isocyanuric acid.

In addition, as the compound of formula (12), for example, dimethyl monocarboxyethyl isocyanuric acid, diethyl monocarboxyethyl isocyanuric acid, diallyl carboxyethyl isocyanuric acid, diallyl carboxyethyl isocyanuric acid, Isocyanic acid, dibutyl monocarboxyethyl isocyanuric acid, diphenyl monocarboxyethyl isocyanuric acid, dibenzyl monocarboxyethyl isocyanuric acid.

The composition for forming an antireflection film of the present invention, in order to prevent mixing with the photoresist coated thereon, is preferably crosslinked by heating after coating, and the composition for forming an antireflection film of the present invention may also contain Crosslinker component. As such a crosslinking agent, a melamine compound or a substituted urea compound having a crosslinking substituent called a methylol group or a methoxymethyl group, a polymer compound having an epoxy group, and the like are exemplified. As a cross-linking agent having at least two cross-linking substituents, there are compounds such as methoxymethyl glycoluril or methoxymethyl melamine, preferably tetramethoxymethyl glycoluril or hexyl glycoluril. Oxymethylmelamine. In addition, compounds such as tetramethoxymethylurea and tetrabutoxymethylurea are also mentioned. The amount of the crosslinking agent added varies depending on the coating solvent used, the base substrate used, the desired solution viscosity, the desired film shape, etc., and is 0.001 to 20% by mass in the entire composition, preferably 0.01 to 15% by mass. % by mass, more preferably 0.05 to 10% by mass. These cross-linking agents sometimes undergo cross-linking reactions through self-condensation, but they may also be used with triazinetrione compounds having a hydroxyalkyl structure as a substituent on a nitrogen atom contained in the composition for forming an antireflection film of the present invention, Cross-linking of a triazinetrione oligomer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom or a triazinetrione polymer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom forms a substituent, such as , the hydroxyl group in the above formula (1), formula (2), formula (3), formula (4), formula (5), formula (56), formula (57), formula (58), formula (59) occurs crosslinking reaction.

As a catalyst for promoting the above-mentioned crosslinking reaction in the present invention, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzene Acidic compounds such as formic acid and hydroxybenzoic acid and/or 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyl tosylate ( 2-nitrobenzyltosylate) and other thermal acid generators. The blending amount is, for example, 0.02 to 10% by mass, or, for example, 0.04 to 5% by mass in the total solid content.

In the antireflection film-forming composition of the present invention, a resin having at least one cross-linking substituent selected from hydroxyl, carboxyl, amino, and thiol groups may be added. By adding such a resin, properties such as the refractive index, attenuation coefficient, and etching rate of the antireflection film formed from the antireflection film-forming composition of the present invention can be adjusted. Examples of such resins include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl alcohol, 2- Resins such as hydroxyethyl vinyl ether, acrylic acid, methacrylic acid, etc. as a structural unit. The weight average molecular weight of such a resin may be 500 to 1,000,000, preferably 500 to 500,000, and more preferably 100 to 100,000. The content of such a resin in the antireflection film-forming composition of the present invention is 20% by mass or less, preferably 15% by mass or less, based on the total solid content.

Such resins include, for example, poly-2-hydroxyethyl methacrylate, polyvinyl alcohol, polyacrylic acid, copolymers of 2-hydroxypropyl acrylate and methyl methacrylate, 2-hydroxy acrylate Copolymer of propyl ester and isopropyl methacrylate, copolymer of 2-hydroxypropyl methacrylate and 2,2,2-trichloroethyl methacrylate, 2-hydroxypropyl methacrylate and Copolymer of 2,2,2-trifluoroethyl methacrylate, copolymer of 2-hydroxypropyl methacrylate and 2-chloroethyl methacrylate, 2-hydroxypropyl methacrylate Copolymer with cyclohexyl methacrylate, copolymer of 2-hydroxypropyl methacrylate and n-octyl methacrylate, copolymer of 2-hydroxypropyl methacrylate and vinyl alcohol, methacrylic acid Copolymer of 2-hydroxypropyl methacrylate and acrylic acid, copolymer of 2-hydroxypropyl methacrylate and maleimide, copolymer of 2-hydroxypropyl methacrylate and acrylonitrile, vinyl alcohol and Copolymer of methyl methacrylate, copolymer of vinyl alcohol and maleimide, copolymer of vinyl alcohol and methyl methacrylate, copolymer of 2-hydroxyethyl vinyl ether and ethyl methacrylate Products, copolymers of 2-hydroxyethyl vinyl ether and 2-hydroxypropyl methacrylate, copolymers of methacrylic acid and ethyl methacrylate, copolymers of methacrylic acid and maleimide, etc.

The antireflection film-forming composition of the present invention may contain a photoacid generator in order to match the acidity of the photoresist coated on the upper layer in the photolithography process. As a preferable photoacid generator, for example, onium salt-based acid generators such as bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate can be mentioned. Classes, halogen-containing compounds such as phenyl bis(trichloromethyl)-s-triazine, photoacid generators, benzointosylate, N-hydroxysuccinimidyl trifluoroform Acid-based photoacid generators such as sulfonate esters, etc. The addition amount of the said photo-acid generator is 0.02-3 mass % in total solid content, Preferably it is 0.04-2 mass %.

A light-absorbing compound and a light-absorbing resin may also be added to the antireflection film-forming composition of the present invention. By adding a light-absorbing compound or a light-absorbing resin, properties such as the refractive index, attenuation coefficient, and etching rate of the antireflection film formed from the antireflection film-forming composition of the present invention can be adjusted. As such a light-absorbing compound or a light-absorbing resin, as long as it has a high absorption energy for light in the wavelength region of the photosensitive characteristic of the photosensitive component in the photoresist layer provided on the antireflection film, it can prevent the The standing wave generated by the reflection of the substrate and the diffuse reflection caused by the unevenness of the substrate surface can be used. In addition, the weight average molecular weight of the light-absorbing resin used is 500 to 1,000,000, preferably 500 to 500,000 or 1,000 to 100,000.

These light-absorbing compounds and light-absorbing resins may be used alone or in combination of two or more. The compounding quantity of the light-absorbing compound and the light-absorbing resin in the composition for forming an antireflection film of the present invention is 0.01% by mass or more, 1% by mass to 90% by mass, for example, 1% by mass to 90% by mass of the total solid content. 50% by mass is, for example, 5% by mass to 40% by mass.

As light-absorbing compounds, for example, phenyl compounds, benzophenone compounds, benzotriazole compounds, azo compounds, naphthalene compounds, anthracene compounds, anthraquinone compounds, triazine compounds, triazinetrione compounds, quinoline compounds, compounds etc. Phenyl compounds, naphthalene compounds, anthracene compounds, triazine compounds, triazinetrione compounds are preferably used.

Preference is given to using phenyl compounds having at least one hydroxyl, amino or carboxyl group, naphthalene compounds having at least one hydroxyl, amino or carboxyl group, and anthracene compounds having at least one hydroxyl, amino or carboxyl group.

Examples of phenyl compounds having at least one hydroxyl, amino or carboxyl group include phenol, bromophenol, 4,4'-sulfodiphenol, tert-butylphenol, biphenol, benzoic acid, salicylic acid, hydroxyl Isophthalic acid, phenylacetic acid, aniline, benzylamine, benzyl alcohol, cinnamyl alcohol, phenylalanine, phenoxypropanol, etc.

Naphthalene compounds having at least one hydroxyl, amino or carboxyl group include, for example, 1-naphthoic acid, 2-naphthoic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, naphthaleneacetic acid, 1-hydroxy- 2-Naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthalene, 2,6-naphthalene dicarboxylic acid and the like.

Examples of the anthracene compound having at least one hydroxyl group, amino group or carboxyl group include 9-anthracenecarboxylic acid, 9-hydroxymethylanthracene, 1-aminoanthracene and the like.

As the light-absorbing resin, for example, one having an aromatic ring structure such as a benzene ring, a naphthalene ring, and an anthracene ring, a pyridine ring, a quinoline ring, a thiophene ring, a thiazole ring, a triazine ring, or an oxazole ring in its structure can be used. A resin with an aromatic heterocyclic structure.

As such a light-absorbing resin, a resin having, in its repeating structural unit, at least one aromatic ring structure selected from a benzene ring, a naphthalene ring, and an anthracene ring can be used.

Examples of the resin having a benzene ring include novolak resins, halogenated novolak resins, polystyrene, polyhydroxystyrene, and the like. Moreover, resin containing benzyl acrylate, benzyl methacrylate, styrene, hydroxystyrene, etc. as a structural unit is also mentioned. Examples of such resins include copolymers of benzyl methacrylate and 2-hydroxypropyl methacrylate, copolymers of styrene and 2-hydroxyethyl methacrylate, hydroxystyrene and methyl Copolymers of ethyl acrylate, terpolymers of benzyl methacrylate with 2-hydroxypropyl methacrylate and ethyl methacrylate, styrene with 2-hydroxyethyl methacrylate and methyl Terpolymers of methyl acrylate, etc.

Further, as the resin having a benzene ring, a resin prepared from a melamine compound (trade name Cymel 303) and a benzoguanamine compound (trade name Cymel 1123) disclosed in US Pat. No. 6,323,310 is also exemplified.

Examples of resins having a naphthalene ring and an anthracycline include resins having structural units ((a) to (g)) shown below.

In the antireflection film-forming composition of the present invention, in addition to the above, a rheology modifier, an adhesion assistant, a surfactant, and the like may be further added as needed.

The rheology modifier is mainly added to improve the fluidity of the antireflection film-forming composition, especially in the baking process, to improve the fillability of the antireflection film-forming composition inside the pores. Specific examples include dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate Phthalic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, di-isooctyl adipate, octyl decyl adipate and other adipate derivatives, maleic acid Maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate, etc., oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, etc., or Stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are usually blended in a proportion of less than 30% by mass in the entire composition of the antireflection film-forming composition for photolithography.

The adhesion adjuvant is mainly added to improve the adhesion between the substrate or the photoresist and the composition for forming an antireflection film, and especially to prevent the photoresist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane , dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane and other alkoxysilanes Silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, etc. , silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc., benzotriazole , benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine and other heterocyclic compounds, Or urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion auxiliaries are usually blended in a proportion of less than 5% by mass, preferably less than 2% by mass, of the entire composition of the antireflection film-forming composition for photolithography.

In the antireflection film-forming composition of the present invention, a surfactant may be blended in order to prevent pinholes and streaks and to improve coatability on uneven surfaces. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. , Polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate , Sorbitan Monopalmitate, Sorbitan Monostearate, Sorbitan Monooleate, Sorbitan Trioleate, Sorbitan Tristearate Sorbitan fatty acid esters such as acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Eftop EF301, EF303, EF352 (manufactured by Toichi Chemical Prodaku), Magaface F171, F173 (manufactured by Dainippon Inki Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomo Slim Co., Ltd.), Asahiga Fluorinated surfactants such as DoAG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), silicone Oxyalkylene polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. The compounding amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less, in the entire composition of the antireflection film-forming composition for lithography of the present invention. These surfactants may be added alone or in combination of two or more.

In the present invention, as a solvent for dissolving the above polymer, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl 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, cyclohexyl Ketone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate ester, butyl acetate, ethyl lactate, butyl lactate, etc. These organic solvents may be used alone or in combination of two or more.

Furthermore, high boiling point solvents, such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate, can be mixed and used. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferable from the viewpoint of improving leveling properties.

As the photoresist coated on the upper layer of the antireflection film of the present invention, either negative type or positive type can be used. There are chemically amplified resists containing a photoacid generator and a binder having a group that increases the dissolution rate of alkali by acid decomposition, and chemically amplified resists that contain an alkali-soluble binder and a photoacid generator and improve resistance by acid decomposition. A chemically amplified resist of a low-molecular compound that has an alkali dissolution rate of the etchant, a binder containing a photoacid generator and a group that increases the alkali dissolution rate by acid decomposition, and a resist that improves the alkali dissolution rate by acid decomposition Chemically amplified resists of low-molecular compounds having a high alkali dissolution rate, for example, APEX-E manufactured by Shipley Co., Ltd. can be mentioned. In addition, Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), Proc.SPIE, Vol.3999, 365-374 (2000), etc. ) The fluorine-atom-containing polymer photoresist described in ).

As a developing solution for a positive photoresist having an antireflection film formed using the composition for forming an antireflection film for lithography of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate can be used , sodium metasilicate, ammonia, etc., primary amines such as ethylamine, n-propylamine, etc., secondary amines such as diethylamine, di-n-butylamine, etc., tertiary amines such as triethylamine, methyldiethylamine, etc. Amines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., bases such as cyclic amines such as pyrrole and piperidine of aqueous solution. Furthermore, alcohols, such as isopropanol, and a nonionic surfactant can also be added to the said alkaline aqueous solution in appropriate quantities, and can also be used. Wherein the preferred developer is quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.

Next, the method for forming a photoresist pattern of the present invention will be described. Substrates (for example, silicon/silicon dioxide-coated substrates, silicon nitride substrates, glass substrates, ITO substrates) used in the manufacture of precision integrated circuit elements etc.) by applying an appropriate coating method such as spin coating or coating to form an antireflection film, and then firing (baking) to cure it to form an antireflection film. Here, the thickness of the antireflection film is, for example, 0.01 to 3.0 μm, or, for example, 0.03 to 1.0 μm. In addition, after coating, the firing conditions are, for example, firing at 80 to 250° C. for 0.5 to 120 minutes, or firing at 150 to 250° C. for 0.5 to 10 minutes, for example. Then, by applying a photoresist, exposing through a prescribed mask, developing, rinsing, and drying, a good photoresist pattern can be obtained. If necessary, post-exposure heating (PEB: Post Exposure Bake) can also be performed. Then, the portion of the antireflection film from which the photoresist has been removed by development through the above steps is removed by dry etching, and a desired pattern can be formed on the substrate.

By containing the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, the triazinetrione oligomer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, or having a hydroxyalkyl Composition for forming an antireflection film of a triazinetrione polymer compound as a substituent on a nitrogen atom The antireflection film formed has the property of efficiently absorbing irradiated light having a wavelength of 248 nm, a wavelength of 193 nm, or a wavelength of 157 nm . Therefore, the effect of preventing reflected light reflected from the substrate is high, and as a result, the photoresist pattern of the upper layer can be formed favorably. In addition, from the triazinetrione compound having a hydroxyalkyl structure as a substituent on a nitrogen atom of the present invention, the triazinetrione oligomer compound having a hydroxyalkyl structure as a substituent on a nitrogen atom, or having a hydroxy The antireflection film made from the antireflection film-forming composition of the triazinetrione high molecular compound having the alkyl structure as a substituent on the nitrogen atom contains a large number of heteroatoms (nitrogen atoms, Oxygen atom) structure, so compared with photoresist, it has a great dry etching speed.

In addition, by selecting the structure of the M part contained in the compound of the formula (1) or the structure of the Ar part contained in the substituent represented by the formula (2) and the linking group represented by the formula (4), that is, a benzene ring, a naphthalene The ring structure of the ring or anthracycline and the type and number of substituents on these rings can also adjust the light absorption characteristics, attenuation coefficient, and refractive index of the antireflection film used for irradiating light.

The attenuation coefficient k value of the antireflection film formed from the antireflection film forming composition of the present invention is 0.40 to 0.65, or 0.40 to 0.60, or 0.45 to 0.65 for light having a wavelength of 248 nm. Also, for light having a wavelength of 193 nm, it is 0.20 to 0.60, or 0.25 to 0.60. In addition, for light having a wavelength of 157 nm, it is 0.20 to 0.50, or 0.30 to 0.45, or 0.30 to 0.40.

Furthermore, the antireflection film formed by the composition forming the antireflection film of the present invention can be used as a film with the following functions through different process conditions, that is, the function of preventing reflected light; Resist interaction, prevention of adverse effects on substrates from materials used in photoresists or substances generated when exposure to photoresists, or prevention of substances generated from substrates during exposure or heating Functions such as the bad influence of the substance on the photoresist.

Hereinafter, the present invention will be described more specifically by way of examples and comparative examples, but the present invention is not limited thereto.

Synthesis Example 1

5.0 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 4.8 g of 6-hydroxy-2-naphthoic acid and 0.02 g of benzyl triethyl Ammonium chloride was dissolved in 39 g of propylene glycol monomethyl ether, and reacted at 130° C. for 24 hours to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 3400.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having the substituent formula (35) and an oligomer compound having triazinetrione rings linked by the linker formula (52).

Synthesis example 2

4.0 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 6.1 g of 6-hydroxy-2-naphthoic acid and 0.02 g of benzyltriethyl Ammonium chloride was dissolved in 42 g of propylene glycol monomethyl ether, and reacted at 130° C. for 24 hours to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 1700.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having the substituent formula (35) and an oligomer compound having triazinetrione rings linked by the linker formula (52).

Synthesis example 3

4.0 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 7.2 g of 6-hydroxy-2-naphthoic acid and 0.02 g of benzyl triethyl Ammonium chloride was dissolved in 45 g of propylene glycol monomethyl ether, and reacted at 130° C. for 24 hours to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 1200.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having the substituent formula (35) and an oligomer compound having triazinetrione rings linked by the linker formula (52).

Synthesis Example 4

1.7 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 3.4 g of 6-hydroxy-2-naphthoic acid, and 0.09 g of benzyl triethyl Ammonium chloride was dissolved in 20 g of propylene glycol monomethyl ether, and reacted at 130° C. for 24 hours to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 1200.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having the substituent formula (35) and an oligomer compound having triazinetrione rings linked by the linker formula (52).

Synthesis Example 5

After dissolving 21 g of glycidyl methacrylate and 39 g of 2-hydroxypropyl methacrylate in 242 g of propylene glycol monomethyl ether, the temperature was raised to 70°C. Then, while the reaction solution was kept warm at 70°C, 0.6g of azobisisobutyronitrile was added and reacted at 70°C for 24 hours to obtain a copolymerization of glycidyl methacrylate and 2-hydroxypropyl methacrylate Solutions of polymer compounds. As a result of GPC analysis of the obtained polymer compound, the weight-average molecular weight calibrated by standard polystyrene was 50,000.

In 100g there is the solution of 20g this copolymerization macromolecular compound, add 10g 9-anthracene formic acid, 0.3g benzyltriethylammonium chloride and 41g propylene glycol monomethyl ether, react at 130 ℃ for 24 hours, obtain formula (60) solutions of polymer compounds. In the formula (60), n and m represent the molar ratio of the structural unit monomer, and n+m=1.

Synthesis Example 6

Make 0.70g three-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 2.44g 2,4,6-tribromo-3-hydroxybenzoic acid and After dissolving 0.04 g of benzyltriethylammonium chloride in 12.72 g of propylene glycol monomethyl ether, it was allowed to react at 125° C. for 24 hours after nitrogen substitution to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 1300.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having a substituent formula (30) and an oligomer compound having a triazinetrione ring linked by a linker formula (45).

Synthesis Example 7

2.0 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC), 6.70 g of 3,5-diiodo-2-hydroxybenzoic acid and 0.115 g After benzyltriethylammonium chloride was dissolved in 35.25 g of propylene glycol monomethyl ether, it was allowed to react at 125° C. for 24 hours after nitrogen substitution to obtain an oligomer compound solution. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 2,000.

In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having the substituent formula (32) and an oligomer compound having a triazinetrione ring linked by a linker formula (46).

Synthesis Example 8

After dissolving 2.0g of monoaryl glycidyl isocyanuric acid and 1.2g of monoaryl isocyanuric acid in 13.2g of cyclohexanone, the reaction solution was heated to 120°C while nitrogen gas was circulated in the reaction solution . Then, 0.08 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 21 hours under a nitrogen atmosphere. GPC analysis of the obtained reaction product revealed that the weight-average molecular weight calibrated against standard polystyrene was 5,800.

In addition, it is presumed that the reaction product obtained in this synthesis example contains a compound having the structural unit (61).

Synthesis Example 9

After dissolving 2.0g of monoallyl diglycidyl isocyanuric acid and 1.5g of monophenyl isocyanuric acid in 14.2g of cyclohexanone, the reaction solution was heated to 120°C, while in the reaction solution Nitrogen gas was circulated. Then, 0.08 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 19 hours under a nitrogen atmosphere. As a result of GPC analysis of the obtained reaction product, the weight average molecular weight calibrated with standard polystyrene was 2400.

In addition, it is presumed that the reaction product obtained in this synthesis example contains a compound having a structural unit of formula (62).

Synthesis Example 10

After dissolving 2.0g of monoallyl diglycidyl isocyanuric acid and 1.0g of monomethyl isocyanuric acid in 12.4g of cyclohexanone, the reaction solution was heated to 120°C, while in the reaction solution Nitrogen gas was circulated. Then, 0.08 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 19 hours under a nitrogen atmosphere to obtain a solution containing a reaction product.

In addition, it is presumed that the reaction product obtained in this synthesis example contains a compound having a structural unit of formula (63).

Synthesis Example 11

After dissolving 2.0g of monoallyl diglycidyl isocyanuric acid and 2.2g of monomethyldicarboxybutyl isocyanurate in 17.4g of cyclohexanone, the reaction solution was heated to 120°C while reacting Nitrogen gas was circulated in the liquid. Then, 0.08 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 19 hours under a nitrogen atmosphere. GPC analysis of the obtained reaction product revealed that the weight-average molecular weight calibrated against standard polystyrene was 12,200.

In addition, it is presumed that the reaction product obtained in this synthesis example contains a compound having a structural unit of formula (64).

Synthesis Example 12

0.50 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC) and 1.2 g of monocarboxypropyl dimethyl isocyanate were dissolved in 7.0 g of diisocyanate After adding methyl formamide, the reaction solution was heated to 120° C. while flowing nitrogen gas in the reaction solution. Then, 0.03 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 20 hours under a nitrogen atmosphere to obtain a solution containing a reaction product represented by formula (65).

Synthesis Example 13

1.8 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC) and 4.0 g of monocarboxymethyl dimethyl isocyanate were dissolved in 23.8 g of formosan After the formation of methyl formamide, the reaction liquid was heated to 120° C. while flowing nitrogen gas in the reaction liquid. Then, 0.1 g of benzyltriethylammonium chloride was added as a catalyst, and the mixture was stirred for 20 hours under a nitrogen atmosphere to obtain a solution containing a reaction product represented by formula (66).

Synthesis Example 14

10 g of cresol-novolak resins (manufactured by Asahi Chiba Co., Ltd., trade name ECN1299, weight average molecular weight: 3900) were added to 80 g of propylene glycol monomethyl ether, and dissolved. After adding 9.7 g of 9-anthracenecarboxylic acid and 0.26 g of benzyltriethylammonium chloride to this solution, it was made to react at 105 degreeC for 24 hours, and the resin compound of formula (67) was obtained. GPC analysis of the obtained reaction product revealed that the weight-average molecular weight calibrated against standard polystyrene was 5,600.

Synthesis Example 15

6.8 g of tris-(2,3-epoxypropyl)-isocyanate (manufactured by Nissan Chemical Industry Co., Ltd., trade name TEPIC) and 12.9 g of 3,7-dihydroxy-2-naphthoic acid and 0.37 g of benzyl Triethylammonium chloride was dissolved in 80 g of cyclohexanone, and reacted at 130° C. for 24 hours to obtain an oligomer compound. GPC analysis was performed on the obtained oligomer compound, and as a result, the weight average molecular weight calibrated by standard polystyrene was 1400. In addition, it is presumed that the oligomer compound obtained in this synthesis example contains a triazinetrione compound having a substituent formula (37) and an oligomer compound having a triazinetrione ring linked by a linker formula (53).

Synthesis Example 16

30 g of trifluoroethyl methacrylate, 12.3 g of methacrylic acid, and 4.6 g of 2-hydroxypropyl methacrylate were dissolved in 201 g of propylene glycol monomethyl ether, and the temperature was raised to 60°C. Then, while keeping the reaction liquid at 60°C, 3.3 g of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) was added, and the mixture was reacted at 60°C for 24 hours. The reaction solution is added dropwise into a mixed solvent of water and ethanol, and the precipitated precipitate is filtered to obtain a copolymerized polymer compound of trifluoroethyl methacrylate, methacrylic acid, and 2-hydroxypropyl methacrylate. As a result of GPC analysis of the obtained polymer compound, the weight-average molecular weight calibrated by standard polystyrene was 15,000.

Synthesis Example 17

30 g of trichloroethyl methacrylate and 4.5 g of 2-hydroxypropyl methacrylate were dissolved in 145 g of propylene glycol monomethyl ether, and the temperature was raised to 60°C. Then, while the reaction solution was kept warm at 60°C, 1.7 g of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) was added and reacted at 60°C for 24 hours. The reaction solution was added dropwise into a mixed solvent of water and ethanol, and the precipitate was filtered to obtain a copolymerized polymer compound of trichloroethyl methacrylate and 2-hydroxypropyl methacrylate. As a result of GPC analysis of the obtained polymer compound, the weight-average molecular weight calibrated by standard polystyrene was 11,000.

Synthesis Example 18

21 g of glycidyl methacrylate and 39 g of 2-hydroxypropyl methacrylate were dissolved in 242 g of propylene glycol monomethyl ether, and the temperature was raised to 70°C. Then, while keeping the reaction solution at 70°C, add 0.6g of azobisisobutyronitrile and react at 70°C for 24 hours to obtain a copolymerization of glycidyl methacrylate and 2-hydroxypropyl methacrylate Solutions of polymer compounds. As a result of GPC analysis of the obtained copolymerized polymer compound, the weight-average molecular weight calibrated by standard polystyrene was 50,000. In 100g of the solution with 20g of the polymer compound, add 10g of 9-anthracenecarboxylic acid, 0.3g of benzyltriethylammonium chloride and 41g of propylene glycol monomethyl ether, and react at 130°C for 24 hours to obtain the polymer of formula (68) Compound solution.

Example 1

0.3 g of hexamethoxymethylmelamine (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 303) and 0.03 g of pyridinium p-toluenesulfonate were mixed in 10 g of the solution having 2 g of the oligomer compound obtained in Synthesis Example 1 above, This was dissolved in 20 g of propylene glycol monomethyl ether and 28 g of methyl lactate to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 2

0.3 g of hexamethoxymethylmelamine (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 303) and 0.03 g of pyridinium p-toluenesulfonate were mixed in 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 2 above, This was dissolved in 20 g of propylene glycol monomethyl ether and 28 g of methyl lactate to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 3

0.3 g of hexamethoxymethylmelamine (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 303) and 0.03 g of pyridinium p-toluenesulfonate were mixed in 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis 3 above, and It was dissolved in 20 g of propylene glycol monomethyl ether and 28 g of ethyl lactate to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 4

0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Powda Link 1174) and 0.05 g of p-toluenesulfonic acid were mixed in 10 g of the solution containing 2 g of the polymer compound obtained in Synthesis Example 4 above. Pyridinium was dissolved in 23 g of propylene glycol monomethyl ether and 31 g of methyl lactate to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 5

0.5 g of tetramethoxymethyl glycoluril and 0.05 g of pyridinium p-toluenesulfonate were mixed in 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 6 above, and 56.7 g of propylene glycol monomethyl ether was added and dissolved , forming a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 6

0.5 g of tetramethoxymethyl glycoluril and 0.05 g of pyridinium p-toluenesulfonate were mixed in 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 7 above, and 56.7 g of propylene glycol monomethyl ether was added to dissolve , forming a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 7

0.3 g of hexamethoxymethylmelamine and 0.03 g of p-toluenesulfonic acid were mixed in 6 g of a solution having 1.2 g of the reaction product obtained in Synthesis Example 8 above, and after adding 23.7 g of ethyl lactate, a polyamide with a pore diameter of 0.10 μm was used. After filtering through an ethylene microporous filter and then using a polyethylene microporous filter with a pore size of 0.05 μm, a composition solution for forming an antireflection film was prepared.

Embodiment 8 to Embodiment 12

In the same manner as above, 0.3 g of hexamethoxymethylmelamine and 0.03 g of p-toluenesulfonic acid were mixed with 6 g of the solution containing 1.2 g of the reaction product obtained in Synthesis Example 9 to Synthesis Example 13, and 23.7 g of ethyl lactate was added. Thereafter, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 13

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.05 g of pyridinium p-toluenesulfonate were added. Onium, 20g propylene glycol monomethyl ether, 59g ethyl lactate and 12g cyclohexanone form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 14

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.4 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170), 0.1 g of hexamethoxymethyl glycoluril, and 0.1 g of hexamethoxymethyl glycoluril were added. Melamine (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 303), 0.05 g of pyridinium p-toluenesulfonate, 16 g of propylene glycol monomethyl ether, 49 g of ethyl lactate, and 8 g of cyclohexanone were prepared into a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 15

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.3 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170), 0.2 g of hexamethoxymethyl glycoluril, and 0.2 g of hexamethoxymethyl glycoluril were added. Melamine (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 303), 0.05 g of pyridinium p-toluenesulfonate, 16 g of propylene glycol monomethyl ether, 49 g of ethyl lactate, and 8 g of cyclohexanone were prepared into a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 16

To 10 g of a solution containing 2 g of the oligomer compound obtained in Synthesis Example 15 above, 2.0 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.2 g of pyridinium p-toluenesulfonate were added. Onium, 14g propylene glycol monomethyl ether, 43g ethyl lactate and 6g cyclohexanone to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 17

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.05 g of 5-sulfowater were added. Cylic acid, 12g propylene glycol monomethyl ether, 37g ethyl lactate and 4g cyclohexanone, form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 18

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.09 g of dinonylnaphthalenesulfonate were added. acid ester, 12g propylene glycol monomethyl ether, 37g ethyl lactate and 4g cyclohexanone to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 19

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.05 g of pyridinium p-toluenesulfonate were added. Onium, 0.09 g of the polymer compound obtained in Synthesis Example 16 above, 10 g of propylene glycol monomethyl ether, 30 g of ethyl lactate, and 2 g of cyclohexanone were used to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 20

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Cymel 1170) and 0.05 g of pyridinium p-toluenesulfonate were added. Onium, 0.18 g of the polymer compound obtained in Synthesis Example 17 above, 10 g of propylene glycol monomethyl ether, 30 g of ethyl lactate, and 2 g of cyclohexanone were used to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Example 21

To 10 g of a solution having 2 g of the oligomer compound obtained in Synthesis Example 15 above, 0.8 g of tris-(2,3-epoxypropyl)-isocyanurate (manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC) was added. , 39g propylene glycol monomethyl ether, 47g propylene glycol monomethyl ether acetate form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Comparative example 1

0.5 g of tetramethoxymethyl glycoluril (manufactured by Mitsui Cytec Co., Ltd., trade name Powerlink 1174) and 0.03 g of p-toluenesulfonic acid were mixed in 10 g of the solution having 2 g of the polymer compound obtained in Synthesis Example 5 above. , and dissolved in 37.3 g of propylene glycol monomethyl ether and 19.4 g of cyclohexanone to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Comparative example 2

0.53 g of hexamethoxymethylmelamine and 0.05 g of pyridinium p-toluenesulfonate monohydrate were mixed in 10 g of a solution having 2 g of the resin obtained in Synthesis Example 14 above, and dissolved in 14.3 g of ethyl lactate, 1.13 g of propylene glycol After monomethyl ether and 2.61 g of cyclohexanone form a 9% solution, filter it with a polyethylene microfilter with a pore size of 0.10 μm, and then filter it with a polyethylene microfilter with a pore size of 0.05 μm to obtain A composition solution for forming an antireflection film was prepared.

Comparative example 3

0.3 g of hexamethoxymethylmelamine, 0.01 g of p-toluenesulfonic acid, 37.3 g of propylene glycol monomethyl ether and 19.4 g of propylene glycol monomethyl ether acetate were added to 10 g of a solution having 2 g of the polymer compound obtained in Synthesis Example 18 above. , allowing it to form a solution. Then, filtration was performed using a polyethylene microfilter with a pore diameter of 0.10 μm, and further filtration was performed using a polyethylene microfilter with a pore diameter of 0.05 μm to prepare a composition solution for forming an antireflection film.

Dissolution test into photoresist solvent

The antireflection film-forming composition solutions prepared in Examples 1 to 21 and Comparative Examples 1 to 3 were applied on silicon wafers by spin coating. On a hot plate, it was baked at 205° C. for 1 minute to form an antireflection film (thickness: 0.10 μm). This antireflection film was dipped in a solvent used for photoresists, for example, ethyl lactate and propylene glycol monomethyl ether, and it was confirmed that it was insoluble in the solvent.

Mixed test with photoresist

The antireflection film-forming composition solutions prepared in Examples 1 to 6, 13 to 21 and Comparative Examples 1 and 3 were applied onto silicon wafers by spin coating. On a hot plate, heating and firing were carried out at 205° C. for 1 minute to form an antireflection film (thickness: 0.10 μm). On the upper layer of the antireflection film for lithography, a commercially available photoresist solution (manufactured by Shipley Co., Ltd., trade name UV113, etc.) was applied by spin coating. After heating at 120° C. for 1 minute on a hot plate and exposing the photoresist, post-exposure heating (PEB: Post Exposure Bake) was performed at 115° C. for 1.5 minutes. After the photoresist was developed, the thickness of the antireflection film was measured, and the antireflection film for photolithography obtained from the composition solution for forming an antireflection film prepared in Examples 1 to 6, 13 to 21 and Comparative Examples 1 and 3 was confirmed. No mixing of the reflective film with the photoresist layer occurred.

Similarly, on the upper layer of the antireflection film (film thickness 0.23 μm) formed by the composition solution for forming the antireflection film prepared by Examples 7 to 9 and Comparative Example 2, a commercially available photoresist solution (manufactured by Sumitomo Chemical Industries, Ltd., trade name PAR710) was applied by spin coating. After heating at 90° C. for 1 minute on a hot plate and exposing the photoresist, post-exposure heating (PEB: Post Exposure Bake) was performed at 90° C. for 1.5 minutes. After the photoresist was developed, the thickness of the antireflection film was measured, and it was confirmed that the antireflection film for lithography obtained from the composition solution for forming an antireflection film prepared in Examples 7 to 9 and Comparative Example 2 did not interfere with light. Mixing of resist layers.

Optical parameter test

The antireflection film-forming composition solutions prepared in Examples 1 to 4, 13 to 21 and Comparative Examples 1 and 3 were applied on silicon wafers by spin coating. On a hot plate, it was baked at 205° C. for 1 minute to form an antireflection film (film thickness: 0.06 μm). Then, the refractive index (n value) and attenuation coefficient (k value) of these antireflection films at a wavelength of 248 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 2 and Table 5.

The solution of the composition for forming an antireflection film prepared in Examples 5 and 6 was applied on a silicon wafer by spin coating. On a hot plate, it baked at 205 degreeC for 1 minute, and formed the antireflection film (film thickness 0.06 micrometer). Then, the refractive index (n value) and attenuation coefficient (k value) of these antireflection films at a wavelength of 157 nm were measured using a spectroscopic ellipsometer (manufactured by J.A. Woolam, VUV-VASE VU-302). Table 3 shows the evaluation results.

The antireflection film-forming composition solutions prepared in Examples 7 to 12 and Comparative Example 2 were applied on silicon wafers by spin coating. On a hot plate, heating and firing were carried out at 205° C. for 1 minute to form an antireflection film (film thickness: 0.09 μm). Then, the refractive index (n value) and attenuation coefficient (k value) of these antireflection films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 4.

Determination of Dry Etching Rate

The antireflection film-forming composition solutions prepared in Examples 1 to 21 and Comparative Examples 1 to 3 were applied on silicon wafers by spin coating. On a hot plate, it was baked at 205° C. for 1 minute to form an antireflection film. Then, the dry etching rate was measured using RIE ES401 manufactured by Nippon Cyntefitsuk under the condition of using CF as the dry etching gas.

Also, a photoresist solution (manufactured by Shipley, trade name UV113 and Sumitomo Chemical Co., Ltd., trade name PAR710) was similarly spin-coated on a silicon wafer to form a coating film. Then, the dry etching rate was measured using RIE ES401 manufactured by Nippon Cyntefitsuk under the condition of using CF as the dry etching gas. The dry etching rate comparison of the antireflection film of Examples 1-4, 13-21 and Comparative Examples 1 and 3 and the photoresist manufactured by Shipley Co., Ltd., brand name UV113 was performed. The results are shown in Table 2 and Table 5. The dry etching rates of the antireflection films of Examples 5 to 12 and Comparative Example 2 and Sumitomo Chemical Co., Ltd. product, brand name PAR710 were compared. The results are shown in Table 3 and Table 4.

Simulation test of the first minimum film thickness

Refractive index n value and attenuation coefficient k value at a wavelength of 248 nm of an antireflection film for lithography obtained from the antireflection film forming composition solution prepared in Examples 1 to 4, 13 to 21 and Comparative Examples 1 and 3 , carry out a simulation test, and calculate the first minimum film thickness and the reflectance when used with the first minimum film thickness. In addition, the simulation test used PROLITH/2 manufactured by FINLE Technologies Inc. The results are shown in Table 2 and Table 5.

Table 2

table 3

Table 4

table 5

It can be judged that the antireflection film obtained by the composition forming the antireflection film of the present invention is 248nm (embodiment 1～4, embodiment 13～21), 157nm (embodiment 5,6) and 193nm ( The light of Examples 7 to 12) has sufficiently effective refractive index and attenuation coefficient.

In addition, it can be judged that the photoresist has a large selectivity ratio of dry etching speed (embodiments 1-21). In addition, compared with the existing anti-reflection film, its anti-reflection effect is high, and it can be used as a thin film. (Examples 1 to 4 and Comparative Example 1, and Examples 13 to 21 and Comparative Example 3) were used. Therefore, the time required for removing the antireflection film by dry etching can be shortened, and thus the undesirable phenomenon of reduction in film thickness of the photoresist layer accompanying removal of the antireflection film by dry etching can be suppressed.

As described above, according to the present invention, it is possible to provide a composition for forming an antireflection film, which is used to form a composition that exhibits good light absorption for light of a wavelength used in the manufacture of semiconductor devices and has a high antireflection film. Light effect, compared with the photoresist layer, it has a large etching speed, does not mix with the photoresist layer, and has no diffusion into the resist during heating and drying. Excellent bottom-type organic anti-reflection membrane.

Claims (16)

1. composition that forms antireflection film, it is characterized in that, contain have the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, have the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the hydroxy alkyl structure as the substituent triazinetrione macromolecular compound on the nitrogen-atoms

Above-mentioned have the hydroxy alkyl structure and as the substituent triazinetrione compound on the nitrogen-atoms be, the compound shown in the formula (1), or have the substituting group shown in formula (2) or the formula (3) as the substituent triazinetrione compound on the nitrogen-atoms,

A in the formula ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, X represents-OC (=O)-,-S-,-O-or-NR-, here R represents hydrogen atom or methyl, M represents to be that 1～6 alkyl, phenyl, naphthyl, halogen atom, carbon number are that 1～6 alkoxy carbonyl, nitro, cyano group, carbon number are that 1～6 alkoxy or carbon number are phenyl ring, naphthalene nucleus or the anthracene nucleus that 1～6 alkylthio group replaces by carbon number

A in the formula ₁, A ₂And A ₃Same as described above, Y represent direct key or-C (=O)-, Ar represents to be that 1～6 alkyl, phenyl, naphthyl, halogen atom, carbon number are that 1～6 alkoxy carbonyl, nitro, carboxyl, cyano group, carbon number are that 1～6 alkoxy, hydroxyl, mercapto, carbon number are 1～6 alkyl sulfenyl or amino phenyl ring or the naphthalene nucleus that replaces by carbon number, R ₁The expression carbon number is 1～6 alkyl, phenyl or benzyl, R ₂Expression hydrogen atom, carbon number are 1～6 alkyl, phenyl or benzyl,

Above-mentioned have the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the hydroxy alkyl structure and as the substituent triazinetrione macromolecular compound on the nitrogen-atoms be, triazinetrione oligomer compounds or triazinetrione macromolecular compound with structure that at least two triazinetrione rings connect by the connection base shown in formula (4) or the formula (5) on its nitrogen-atoms

A in the formula ₁, A ₂And A ₃Same as described above, Y represent direct key or-C (=O)-, Ar represents to be that 1～6 alkyl, phenyl, naphthyl, halogen atom, carbon number are that 1～6 alkoxy carbonyl, nitro, carboxyl, cyano group, carbon number are that 1～6 alkoxy, hydroxyl, mercapto, carbon number are 1～6 alkyl sulfenyl or amino phenyl ring or the naphthalene nucleus that replaces by carbon number, Q represent carbon number be 1～6 alkyl, carbon number be 5～8 naphthenic base, Ar or-CH ₂-Ar-CH ₂-, R ₁The expression carbon number is 1～6 alkyl, phenyl or benzyl.

2. the composition of formation antireflection film as claimed in claim 1, it is above-mentioned that to have the substituent triazinetrione compound shown in formula (2) or the formula (3) be the compound with the structure shown in formula (6) or the formula (7),

A in the formula ₁, A ₂, A ₃, Y, Ar, R ₁And R ₂Described identical with claim 1.

3. the composition of formation antireflection film as claimed in claim 1, above-mentioned triazinetrione oligomer compounds or triazinetrione macromolecular compound with structure that at least two triazinetrione rings connect by the connection base shown in formula (4) or the formula (5) on its nitrogen-atoms is, compound with the structure shown in formula (8) or the formula (9)

A in the formula ₁, A ₂, A ₃, Y, Ar, Q and R ₁Described identical with claim 1.

4. the composition of formation antireflection film as claimed in claim 1, above-mentioned have the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the hydroxy alkyl structure and as the substituent triazinetrione macromolecular compound on the nitrogen-atoms be, the resultant of reaction of compound shown in compound shown in the formula (10) and formula (11) or the formula (12)

R in the formula ₃The expression carbon number is that 1～6 alkyl, carbon number are 3～6 alkenyl, phenyl, benzyl or 2,3-glycidyl, R ₄And R ₅The expression carbon number is that 1～6 alkyl, carbon number are 3～6 alkenyl, phenyl or benzyl, R ₆The expression carbon number be 1～6 alkyl, phenyl, benzyl or-(CH ₂) _nCOOH, n represent 1,2 or 3.

5. the composition of formation antireflection film as claimed in claim 1, it is characterized in that, above-mentioned have the substituting group shown in the formula (2) as the substituent triazinetrione compound on the nitrogen-atoms or triazinetrione oligomer compounds or triazinetrione macromolecular compound with structure that at least two triazinetrione rings connect by the connection base shown in the formula (4) on its nitrogen-atoms be, by having at least having shown in two triazinetrione compounds that on nitrogen-atoms, have a substituent nitrogen-atoms shown in the formula (13) and the formula (14) to be selected from identical or different at least two substituent phenyl compounds of carboxyl and hydroxyl or the compound that naphthalene compound produces

HO-γ-Ar-γ-OH (14)

A in the formula (13) ₁, A ₂And A ₃Described identical with claim 1, Y is described identical with claim 1 with Ar in the formula (14).

6. the composition of formation antireflection film as claimed in claim 5, above-mentioned have two triazinetrione compounds that have the substituent nitrogen-atoms shown in the formula (13) on nitrogen-atoms at least and be the triazinetrione compound shown in the formula (15)

A in the formula ₁, A ₂, A ₃Described identical with claim 1.

7. the composition of formation antireflection film as claimed in claim 5, the phenyl compound or the naphthalene compound of above-mentioned formula (14) be, is selected from least one compound in the compound shown in formula (16)～(21),

B represents that hydrogen atom, carbon number are that 1～6 alkyl, phenyl, naphthyl, halogen atom, carbon number are that 1～6 alkoxy carbonyl, nitro, carboxyl, cyano group, carbon number are that 1～6 alkoxy, hydroxyl, mercapto, carbon number are 1～6 alkyl sulfenyl or amino in the formula, n represents 1～6 number, m represents 1～4 number, and n, m be more than or equal to 2 several the time, B can be the same or different.

8. as the composition of each described formation antireflection film of claim 1～7, also contain and have at least two and be cross-linked to form substituent crosslinking chemical.

9. as the composition of each described formation antireflection film of claim 1～7, also contain acid and/or acid-producing agent.

10. as the composition of each described formation antireflection film of claim 1～7, also contain and have at least one that be selected from hydroxyl, carboxyl, amino and the mercapto and be cross-linked to form substituent resin.

11. antireflection film, by the composition of each described formation antireflection film of claim 1～10 is coated on the semiconductor substrate, burn till form antireflection film after, be that the attenuation coefficient k value of this antireflection film of the light of 248nm is 0.40～0.65 to wavelength.

12. antireflection film, by the composition of each described formation antireflection film of claim 1～10 is coated on the semiconductor substrate, burn till form antireflection film after, be that the attenuation coefficient k value of this antireflection film of the light of 193nm is 0.20～0.60 to wavelength.

13. the formation method of the antireflection film of a manufacturing that is used for semiconductor devices obtains by the composition of each described formation antireflection film of claim 1～10 being coated on the substrate, being burnt till.

14. the formation method of an antireflection film that in the manufacturing of the semiconductor devices that the light that uses wavelength 248nm or wavelength 193nm carries out, uses, by the composition of each described formation antireflection film of claim 1～10 is coated on the substrate, burn till acquisition.

15. the formation method of a photoresist figure that uses in the manufacturing of semiconductor devices comprises following operation: coat the composition of each described formation antireflection film of claim 1～10 on the substrate and burn till the operation that forms antireflection film; On this antireflection film, form the operation of photoresist layer; The operation of the semiconductor-based board to explosure of antireflection film and photoresist layer will be coated with; The operation of after exposure, the photoresist layer being developed.

16. the formation method of photoresist figure as claimed in claim 15, above-mentioned exposure are to utilize the light of 248nm or 193nm wavelength to carry out.