CN100547487C

CN100547487C - The photoetching composition that forms antireflection film

Info

Publication number: CN100547487C
Application number: CNB2003801053881A
Authority: CN
Inventors: 岸冈高广; 水沢贤一; 榎本智之; 坂本力丸; 中山圭介; 河村保夫
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2002-10-09
Filing date: 2003-10-08
Publication date: 2009-10-07
Anticipated expiration: 2023-10-08
Also published as: CN1723418A

Abstract

The invention provides a kind of composition that forms antireflection film, it is used for the light of the wavelength that uses in the manufacturing of semiconductor devices is shown good light absorption, have very high antireflection light effect, comparing with the photoresist layer has bigger etching speed organic anti-reflective film.Particularly, the invention provides a kind of composition that forms antireflection film, it is characterized in that, contain and have the hydroxy alkyl structure as substituent triazinetrione compound, oligomer compounds or macromolecular compound on the nitrogen-atoms.

Description

The photoetching composition that forms antireflection film

Technical field

The present invention relates to antireflection film material composition, specifically, relate to a kind of composition that forms antireflection film, this antireflection film reduces to the reflection of the exposure irradiation light of coating the photoresist layer irradiation on the substrate from substrate in the photoetching process that semiconductor devices is made.More particularly, relate to a kind of composition that forms antireflection film, it contains in the photoetching process that the semiconductor devices that the exposure reflected light that uses wavelength 248nm, 193nm or 157nm carries out is made, and absorbs effectively from catoptrical compound, oligomer or the macromolecular compound of substrate reflection.

Background technology

All the time, in the manufacturing of semiconductor devices, people utilize to have used the photoetching of photo-corrosion-resisting agent composition to carry out microfabrication.Above-mentioned microfabrication is; on the semiconductor substrate of silicon wafer etc., form the film of photo-corrosion-resisting agent composition; on this film, see through the active ray of the mask graph irradiation ultraviolet radiation etc. of the figure describe semiconductor devices; develop, as diaphragm semiconductor substrate is carried out the processing method of etch processes with the photoresist figure that obtains.But, in recent years, the highly integrated continuous development of semiconductor devices, the active ray of use also has from i line (wavelength 365nm), KrF excimer laser (wavelength 248nm) tendency to the short wavelengthization of ArF excimer laser (wavelength 193nm) conversion.Accompany therewith, active ray becomes big problem gradually from the diffuse reflection of semiconductor substrate, the influence of standing wave.Therefore, the method that antireflection film (bottom anti-reflective coating Bottom Anti-reflective Coating:BARC) is set between photoresist and semiconductor substrate is widely studied day by day.

As antireflection film, the inorganic antireflection film of known titanium, titania, titanium nitride, chromium oxide, carbon, α-silicon etc. and comprise the organic anti-reflective film of light absorptive material and macromolecular compound.The former, the equipment of the true evaporation coating device of needs, CVD device, sputter equipment etc. when forming film, relative therewith, the latter is favourable not needing on the special equipment this point, and has been carried out big quantity research.For example can list, in with a part, have acryl resin type antireflection film, in a part, have as the hydroxyl of crosslinking reactive group and (for example, with reference to patent documentation 1, the patent documentations 2) such as phenolic novolac type antireflection films of extinction group as the hydroxyl of crosslinking reactive group and extinction group.

As the required rerum natura of organic anti-reflective membrane material, there are pair light or radioactive ray to have very big absorbance, do not produce mix (being insoluble to the photoresist solvent) with the photoresist layer, not low molecular diffusion thing is from the diffusion of antireflection film material to the resist of coating thereon when coating or heat drying, have (for example, with reference to non-patent literature 1, non-patent literature 2, non-patent literatures 3) such as dry etching rate also bigger than photoresist.

In recent years, in the photoetching process of having used KrF excimer laser, ArF excimer laser, the miniaturization of processing dimension, that is, the miniaturization of the photoresist dimension of picture of formation develops gradually.Along with the development of the miniaturization of photoresist figure, in order to prevent collapsing of photoresist figure etc., people also begin to expect to realize the filming of photoresist gradually.And when photoresist is used with film, in order to be suppressed at together the etched reduction of removing the thickness of the photoresist layer in the operation that utilizes of the organic anti-reflective film that uses, people are expecting to utilize the etched organic anti-reflective film of removing the shorter time.That is, realize short timeization, require and compared the organic anti-reflective film that can form of film uses in the past or had than the organic anti-reflective film of etching speed selection ratio also big and photoresist in the past in order to make etching remove operation.

But the Study on Technology of antireflection film up to now mainly is about having used wavelength to carry out as the photoetching process of the irradiates light of 365nm, 248nm, 193nm.And in such research, develop extinction composition, the extinction group of the light that absorbs each wavelength effectively gradually, and its composition as organic system antireflection film composition is used.For example, about the irradiates light of 365nm, the chalcone dyestuff that known 4-hydroxy acetophenone and the condensation of 4-methoxybenzaldehyde are generated is effective (for example, with reference to patent documentation 3); About the irradiates light of 248nm, the known naphthyl polymkeric substance that contains with specific structure shows very big absorbance (for example, with reference to patent documentation 4); About the irradiates light of 193nm, the known resinous binder compositions that contains the phenyl unit is excellent (for example, with reference to patent documentation 5).

Known in addition, the technology that three (hydroxy alkyl) isocyanuric acid ester that aromatics or fatty compound are replaced is used for the wide area ultraviolet light absorber (for example, with reference to patent documentation 6), and the known hardening composition (for example, with reference to patent documentation 7) that contains cyanuric acid as the polymerism organic compound.In addition, also known antireflection film composition (for example, with reference to patent documentation 8) about containing the cyanuric acid derivant.In addition, disclose by 1,3, the synthetic polyester of 5-three (2-hydroxyethyl) cyanuric acid is used to antireflection film (for example, with reference to patent documentation 9, patent documentation 10).

In recent years, proposition will have been used the more photoetching process of the F2 excimer laser of short wavelength's light source (wavelength 157nm) irradiates light of conduct, as the next-generation technology of the technology of having used ArF excimer laser (wavelength 193nm).Think and utilize this technology can carry out the microfabrication of processing dimension, now, just carrying out positive development research from aspects such as device, materials smaller or equal to 100nm.But the fact is, about the research of material, major part is about photoresist, is unknown substantially about the research of organic system antireflection film.Its reason is, absorbing wavelength is the composition of the light of 157nm effectively, that is, the extinction composition that has strong absorption band at 157nm is unknown substantially.

Owing to think in the photoetching process of having used F2 excimer laser (wavelength 157nm) irradiates light, processing dimension will be less than and equal 100nm, therefore, from the requirement of asperratio, think photoresist can with thickness be that the form that the existing film of 100～300nm is in a ratio of film is used.To the organic system antireflection film that the photoresist with such film uses, requirement can be used with film, and to the selectivity height of the dry ecthing of photoresist.In addition, for the organic system antireflection film can use with the film of 30～80nm, thinking needs the big antireflection film of attenuation coefficient k value.In the simulation test of having used PROLITHver.5 (the LithoTechJapan system: the optical constant of photoresist (refractive index, attenuation coefficient) is used the ideal value of anticipation), can obtain following result: making basal substrate is in the situation of silicon, as thickness is the antireflection film of 30～80nm, can use its thickness is the film of second minimum thickness (about 70nm), and at this moment, attenuation coefficient k value has from the reflectivity of substrate for smaller or equal to 2% sufficient anti-reflection effect in 0.3～0.6 scope.In addition, according to same simulation test, obtain following result: monox is being used for basal substrate, make in the situation that the monox thickness changes in 100nm～200nm, when the thickness of antireflection film is 70nm, in order to obtain sufficient anti-reflection effect, attenuation coefficient k value must be 0.4～0.6.For example, be 0.2 o'clock in attenuation coefficient k value, change between 5%～10% from the reflectivity of substrate, be 0.4 o'clock in attenuation coefficient k value, change 0～5% from the reflectivity of substrate.Can think like this in order to obtain sufficient anti-reflection effect, attenuation coefficient k value is necessary it is big value, for example is more than or equal to 0.3, but the organic system antireflection film material that satisfies such attenuation coefficient k value is unknown substantially.

By this fact,, has the organic system antireflection film of excellent antireflection light effect even the expectation exploitation also can absorb the reflected light from substrate effectively in the photoetching process of the irradiates light that has used wavelength 157nm.And then now, people cause resist research to the lithography process of the irradiates light that used the F2 excimer laser energetically, can think from now on, should be able to develop multiple photoresist.Can think in addition, cooperate the various requirement characteristic of multiple like this photoresist, change the method for the characteristic of antireflection film, for example, change the method for attenuation coefficient k value, it is important to become gradually.

Patent documentation 1: No. 5919599 instructions of United States Patent (USP)

Patent documentation 2: No. 5693691 instructions of United States Patent (USP)

Patent documentation 3: the flat 11-511194 communique of special table

Patent documentation 4: the spy opens flat 10-186671 communique

Patent documentation 5: the spy opens the 2000-187331 communique

Patent documentation 6: the spy opens flat 11-279523 communique

Patent documentation 7: the spy opens flat 10-204110 communique

Patent documentation 8: the international pamphlet that discloses No. 02/086624

Patent documentation 9: european patent application discloses instructions No. 1298492

Patent documentation 10: european patent application discloses instructions No. 1298493

Non-patent literature 1:Tom Lynch and other three people, " Properties and Performanceof Near UV Reflectivity Control Layers ", the U.S., " in Advances in ResistTechnology and Processing XI ", Omkaram Nalamasu volume, SPIE journal, 1994, the 2195th volume, p.225-229

Non-patent literature 2:G.Taylor and other 13 people, " Methacrylate Resist andAntireflective Coatings for 193nm Lithography ", the U.S., " inMicrolithography 1999:Advance in Resist Techology and Processing XVI ", Will Conley volume, SPIE journal,, the 3678th volume in 1999, p.174-185

Non-patent literature 3:Jim D.Meador and other 6 people, " Recent Progress in 193nmAntireflective Coatings ", the U.S., " in Microlithography 1999:Advances inResist Technology and Processing XVI ", Will Conley volume, SPIE journal,, the 3678th volume in 1999, p.800-809

The present invention relates to the composition of a kind of photoetching with the formation antireflection film, it is used for antireflection film, and this antireflection film is the light of 248nm, 193nm or 157nm to short wavelength's light, particularly wavelength, and strong absorption is arranged.In addition, the invention provides a kind of composition that forms antireflection film, it can use in the photoetching process of the semiconductor devices manufacturing that the irradiates light that uses KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) or F2 excimer laser (wavelength 157nm) carries out.In addition, the invention provides a kind of composition that forms antireflection film, it is used for antireflection film for lithography, when the irradiates light with KrF excimer laser, ArF excimer laser or F2 excimer laser is used for microfabrication, this antireflection film for lithography absorbs the reflected light from substrate effectively, does not take place and the mixing of photoresist layer, removing in the operation and can promptly remove subsequently, comparing with photoresist has bigger dry etching rate.The present invention also provides the formation method of antireflection film for lithography of the composition that has used this formation antireflection film and the formation method of photoresist figure.

Disclosure of an invention

The present invention, as the 1st viewpoint is a kind of 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;

As the 2nd viewpoint is composition as the described formation antireflection film of the 1st viewpoint, and above-mentioned to have the hydroxy alkyl structure be the compound (A in the formula shown in the formula (1) as the substituent triazinetrione compound on the nitrogen-atoms 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 can be 1～6 alkyl by carbon number, and 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 alkyl sulfenyl replaces);

As the 3rd viewpoint is composition as the described formation antireflection film of the 1st viewpoint, above-mentioned have the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, has the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the hydroxy alkyl structure and be as the substituent triazinetrione macromolecular compound on the nitrogen-atoms, have the substituting group shown in formula (2) or the formula (3) as the substituent triazinetrione compound on the nitrogen-atoms, or have the triazinetrione oligomer compounds or the triazinetrione macromolecular compound (A in the formula of the structure that at least two triazinetrione rings connect by the connection base shown in formula (4) or the formula (5) on its nitrogen-atoms ₁, A ₂And A ₃Identical with above-mentioned definition, 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, R ₂Expression hydrogen atom, carbon number are 1～6 alkyl, phenyl or benzyl);

As the 4th viewpoint is composition as the described formation antireflection film of the 3rd viewpoint, and above-mentioned to have the substituent triazinetrione compound shown in formula (2) or the formula (3) be the compound (A in the formula with the structure shown in formula (6) or the formula (7) ₁, A ₂, A ₃, Y, Ar, R ₁And R ₂Identical with above-mentioned definition);

As the 5th viewpoint is composition as the described formation antireflection film of the 3rd viewpoint, 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 to have the compound (A in the formula of the structure shown in formula (8) or the formula (9) ₁, A ₂, A ₃, Y, Ar, Q, R ₁And R ₂Identical with above-mentioned definition);

As the 6th viewpoint is composition as the described formation antireflection film of the 1st viewpoint, 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 (R in the formula of compound shown in compound shown in the formula (10) and formula (11) or the formula (12) 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);

As the 7th viewpoint is composition as the described formation antireflection film of the 3rd viewpoint, 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 (formula (13) that naphthalene compound produces, (14) A in ₁, A ₂, A ₃, Y is identical with above-mentioned definition with Ar);

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

As the 8th viewpoint is composition as the described formation antireflection film of the 7th viewpoint, and 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 (A in the formula shown in the formula (15) ₁, A ₂, A ₃Identical with above-mentioned definition);

As the 9th viewpoint is composition as the described formation antireflection film of the 7th viewpoint, the phenyl compound or the naphthalene compound of above-mentioned formula (14) are, (B represents hydrogen atom in the formula to be selected from least a compound in the compound shown in formula (16)～(21), carbon number is 1～6 alkyl, phenyl, naphthyl, halogen atom, carbon number is 1～6 alkoxy carbonyl, nitro, carboxyl, cyano group, carbon number is 1～6 alkoxy, hydroxyl, mercapto, carbon number is 1～6 alkyl sulfenyl or amino, n represents 1～6 number, m represents 1～4 number, and at n, m be more than or equal to 2 several the time, B can be the same or different);

As the 10th viewpoint is composition as each described formation antireflection film of the 1st～the 9th viewpoint, also contains to have at least two and be cross-linked to form substituent crosslinking chemical;

As the 11st viewpoint is as the composition of each described formation antireflection film of the 1st～the 10th viewpoint, also contains acid and/or acid-producing agent;

As the 12nd viewpoint is composition as each described formation antireflection film of the 1st～the 11st viewpoint, also contains to have at least one that be selected from hydroxyl, carboxyl, amino and the mercapto and be cross-linked to form substituent resin;

As the 13rd viewpoint is a kind of antireflection film, by the composition of each described formation antireflection film of the 1st～the 12nd viewpoint 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;

As the 14th viewpoint is a kind of antireflection film, by the composition of each described formation antireflection film of the 1st～the 12nd viewpoint 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 157nm is 0.20～0.50 to wavelength;

As the 15th viewpoint is a kind of antireflection film, by the composition of each described formation antireflection film of the 1st～the 12nd viewpoint 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;

As the 16th viewpoint is a kind of formation method of the antireflection film that uses in the manufacturing of semiconductor devices, obtains by the composition of each described formation antireflection film of the 1st～the 12nd viewpoint being coated on the substrate, being burnt till;

As the 17th viewpoint is a kind of formation method of the antireflection film that uses in the manufacturing of the semiconductor devices that the light that uses wavelength 248nm, wavelength 193nm or wavelength 157nm carries out, obtain by the composition of each described formation antireflection film of the 1st～the 12nd viewpoint being coated on the substrate, being burnt till;

As the 18th viewpoint is a kind of formation method of the photoresist figure that uses in the manufacturing of semiconductor devices, comprise following operation: coat the composition of each described formation antireflection film of the 1st～the 12nd viewpoint on the substrate and burn till, form the operation of 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.

As the 19th viewpoint is formation method as the described photoresist figure of the 18th viewpoint, and above-mentioned exposure is to utilize the light of 248nm, 193nm or 157nm wavelength to carry out.

The best mode that carries out an invention

The present invention relates to a kind of composition that forms antireflection film, it is characterized in that, contain and have the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, has 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, in addition, relate to a kind of composition that forms antireflection film, it can be used to use short wavelength's irradiates light, KrF excimer laser (wavelength 248nm) particularly, the irradiates light of ArF excimer laser (wavelength 193nm) or F2 excimer laser (wavelength 157nm), the photoetching process that the semiconductor devices that carries out is made.

The composition of formation antireflection film of the present invention, basic for comprise 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 and the composition of solvent, be the composition that contains crosslinking catalyst, surfactant etc. as composition arbitrarily.The solid constituent of the composition of formation antireflection film of the present invention for example is 0.1～50% quality, or for example is 0.5～30% quality.Here so-called solid constituent is meant, removes the composition of solvent composition from the composition that forms antireflection film.

In addition, in the composition of formation antireflection film of the present invention, as having the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, has the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the hydroxy alkyl structure and be as the use level of the substituent triazinetrione macromolecular compound on the nitrogen-atoms, in all solids composition of per 100% quality, be more than or equal to 10% quality, it for example is 30% quality～99% quality, for example being 50% quality～99% quality, further for example is 60% quality～95% quality.

In the composition of formation antireflection film of the present invention,, can list the compound shown in the formula (1) as having the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms.A in formula (1) 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, and 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 alkyl sulfenyl replaces by carbon number.

Such formula (1) compound, for example, the compound shown in can through type (15) and the reaction of the compound shown in the formula (22) obtain (in the formula (22), X represents-OC (=O)-,-S-,-O-or-NR-, here R represents hydrogen atom or methyl, and 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 alkyl sulfenyl replaces by carbon number).

The reaction of the compound shown in compound shown in such formula (15) and the formula (22), preferably the solution state with the organic solvent that is dissolved in benzene,toluene,xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-Methyl pyrrolidone etc. carries out.In this reaction, formula (15) compound and formula (22) compound can be distinguished and only use a kind, but also 2 kinds or compound more than it can be used in combination.In addition, in this reaction, the quaternary ammonium salt that can use benzyltriethylammoinium chloride, tetrabutylammonium chloride, tetraethylammonium bromide etc. is as this catalyst for reaction.The temperature of reaction of this reaction, reaction time depend on the compound, concentration of use etc., and the reaction time can suitably be selected in 0.1～100 hour scope, and temperature of reaction can suitably be selected in 20 ℃～200 ℃ scope.When using catalyzer, can be to use in the scope of 0.001～50% quality at all-mass with respect to the compound that uses.

In the composition of the formation antireflection film of the present invention that contains the compound shown in the formula (1), the characteristic of the antireflection film that forms by this composition that forms antireflection film,, be the characteristic that depends on the kind of formula (22) compound that in this reaction, uses greatly particularly to the extinction characteristic of the irradiates light that in photoetching process, uses, attenuation coefficient, refractive index etc.In addition, the kind of the formula of use (22) compound also can be removed the needed time of operation and exerts an influence utilizing of the antireflection film that formed by the composition that forms antireflection film of the present invention is etched.Especially, the substituent kind and the quantity of phenyl ring, naphthalene nucleus or anthracene nucleus in formula (22) compound, etched to remove the needed time of operation influential to utilizing of antireflection film, contain the heteroatomic substituting group of halogen atom, nitrogen-atoms, oxygen atom, sulphur atom etc. or increase this substituent quantity by introducing, can shorten and utilize etched removing the needed time of operation.

When the composition of the formation antireflection film of the present invention that will contain the compound shown in the formula (1) has been applied to use wavelength as the technology of the light of 248nm (KrF excimer laser), preferably use compound (M is naphthalene nucleus or anthracene nucleus) as formula (22) compound with naphthalene nucleus or anthracene nucleus.In addition, be applied to use wavelength as 193nm (ArF excimer laser) and wavelength during, preferably using the have phenyl ring compound of (M is phenyl ring) as the technology of the light of 157nm (F2 excimer laser).

As formula (15) compound that uses in the reaction that is used for acquisition formula (1) compound, for example can list three-(2, the 3-glycidyl)-isocyanuric acid ester, three-(2-methyl-2, the 3-glycidyl)-isocyanuric acid ester, three-(2,3-epoxy butyl)-isocyanuric acid ester etc.

As formula (22) compound that uses in the reaction that is used for acquisition formula (1) compound, for example can list, benzoic acid, the m-phthalic acid mono ethyl ester, 2, the 4-dibromobenzoic acid, the 4-methyl benzoic acid, O-Anisic Acid, 2,3, the 5-Triiodobenzoic acid, 2-chloro-4-nitrobenzoic acid, the 4-fluobenzoic acid, the 4-iodo-benzoic acid, the 4-bromobenzoic acid, the 4-p t butylbenzoic acid, the 3-trifluoromethylbenzoic acid, the 2-nitrobenzoic acid, 4-isopropoxy benzoic acid, the 3-cyanobenzoic acid, the 3-Phenylbenzoic acid, 3-bromo-4-methyl benzoic acid, 2,4,6-tribromo-benzene formic acid, the 4-methylthio-benzoic acid, 2-bromo-4-fluobenzoic acid etc.

In addition, as formula (22) compound, for example can list naphthalene-2-formic acid, 1-bromonaphthalene-2-formic acid, 4-bromo-3-methoxyl-naphthalene-2-formic acid, 3-methylnaphthalene-2-formic acid, 4-fluoronaphthalene-1-formic acid, 4-nitronaphthalene-1-formic acid, 5-bromonaphthalene-1-formic acid, 8-iodine naphthalene-1-formic acid, anthracene-9-formic acid, anthracene-2-formic acid, 10-bromine anthracene-9-formic acid etc.

In addition, as formula (22) compound, for example can list, phenol, the 4-methylphenol, the 4-chlorophenol, the 4-bromophenol, the 4-nitrophenol, 2,3,4,5-tetrabromo phenol, pentabromophenol, 4-bromo-2-fluorophenol, the 4-iodophenol, 2,4, the 6-iodophenisic acid, 2,5-dimethyl-4-iodophenol, the 4-methylthiophenol, the 3-metoxyphenol, the 3-bromophenol, the 2-cyanophenol, 2,6-two iodo-4-cyanophenols, the 3-methyl hydroxybenzoate, beta naphthal, 1-bromo-beta naphthal, 2-nitro-1-naphthols, 2-methyl isophthalic acid-naphthols, 4-methoxyl-1-naphthols, 2, the 4-dichloro-1-naphthol, 2 hydroxy naphthalene-3-methyl formate, 2-hydroxyl anthracene, hydroxy-anthracene-9 etc.

In addition, as formula (22) compound, for example can list, aniline, 3-chloroaniline, 2-bromaniline, 4-Iodoaniline, 3-aminoanisole, 3-methyl mercapto aniline, 4-nitroaniline, 3-isopropyl aniline, 3,5-dibromo aniline, 2-fluoro-4-Iodoaniline, 2-amino-5-iodo-benzoic acid methyl esters, 2,4,6-tribromaniline, 4-bromo-3-methylaniline, 2-bromo-4-nitroaniline, 2-bromo-5-5-trifluoromethylaniline, 3-phenylaniline, 1-amino naphthalenes, 1-amino-4-bromonaphthalene, 1-amino-2-nitronaphthalene, 1-amino anthracene, 9-amino anthracene etc.

Further, as formula (22) compound, for example can list benzenethiol, 2-methylbenzene thiophenol, 4-chlorothio-phenol, reptazin, 3-methoxybenzenethiol 3-bromo thiophenol, 2-mercaptobenzoic acid methyl esters, 4-nitro thiophenol, 3-iodobenzene thiophenol, 1-thionaphthol, 9-sulfydryl anthracene etc.

In addition, as with the compound of formula (8) compound reaction, except formula (15) compound, in addition, for example, can also use thiophene-2-carboxylic acid, 5-bromothiophene-2-formic acid, phenylacetic acid, 4-bromobenzene ethoxyacetic acid, phenmethylol, 2, the compound with carboxyl, hydroxyl of 4-dibromobenzene methyl alcohol, 3-bromo cinnamic acid, 9-hydroxymethyl anthracene, thiazole-2-formic acid, 2-amino-5-bromo thiazole etc.

The formula that contains in the composition as formation antireflection film of the present invention (1) compound for example can list, the compound of following formula (23) (the compound sequence number 1 in the following table 1), following formula (24) (the compound sequence number 15 in the following table 1).

Equally, can also list the compound shown in the table 1 (Ph represents phenyl in the table, and 1-Nap represents the 1-naphthyl, and 2-Nap represents the 2-naphthyl, and 9-Ant represents the 9-anthryl).

Table 1

In the composition of formation antireflection film of the present invention, the compound shown in the formula (1) can use separately, also can or be used in combination more than it 2 kinds.As the use level of such formula (1) compound, be more than or equal to 10% quality in all solids composition, for example, be 30% quality～99% quality, for example be 50% quality～99% quality, and then for example be 60% quality～95% quality.

In the composition of formation antireflection film of the present invention, as have the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, can also list have the substituting group shown in formula (2) or the formula (3) as the substituent triazinetrione compound on the nitrogen-atoms, 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.In formula (2), (3), (4), (5), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, 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, R ₂Expression hydrogen atom, carbon number are 1～6 alkyl, phenyl or benzyl.

Have the substituting group shown in the formula (2) as the substituent triazinetrione compound on the nitrogen-atoms as above-mentioned, can use compound with structure shown in the formula (6).In the formula (6), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, 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.

The compound of formula (6) can have formula (13) by making on nitrogen-atoms

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

(in the formula, A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively) shown in substituent triazinetrione compound and formula (14) (in the formula, Y represent direct key or-phenyl compound shown in the 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) or naphthalene compound react and obtain.In this reaction, the compound shown in the formula (14) can only use a kind of, in addition, also two kinds or compound more than it can be used in combination.This reaction is preferably carried out with the solution state of the organic solvent that is dissolved in benzene,toluene,xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-Methyl pyrrolidone etc.In addition, also the quaternary ammonium salt of benzyltriethylammoinium chloride, tetrabutylammonium chloride, tetraethylammonium bromide etc. can be used as this catalyst for reaction.The temperature of reaction of this reaction, reaction time depend on the compound, concentration of use etc., and the reaction time can suitably be selected from 0.1～100 hour scope, and temperature of reaction can suitably be selected from 20 ℃～200 ℃ scope.In using the occasion of catalyzer, catalyzer can be to use in the scope of 0.001～50% quality at the all-mass with respect to the compound that uses.

As on nitrogen-atoms, having the substituent triazinetrione compound shown in the formula (13), have as can be known and have one, two or three have the situation of the substituent nitrogen-atoms of formula (13) on nitrogen-atoms, and can use in them any one in the present invention, or also they can be used in combination.The preferred substituent compound that uses with three formulas (13), that is, and the compound shown in the formula (15).In the formula (15), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, preferably use A ₁, A ₂And A ₃Be the compound of hydrogen atom, A ₁And A ₃Be hydrogen atom, A ₂Compound for methyl.

In this reaction, when use has the triazinetrione compound of two or three substituent nitrogen-atoms with formula (13), have as can be known its whole substituting groups and formula (14) compound reaction situation and have only one of them or situation that the compound of two substituting groups and formula (14) reacts, and the triazinetrione compound that uses in the composition of formation antireflection film of the present invention is the compound that comprises its any situation.In the composition of formation antireflection film of the present invention, the preferred whole substituting groups of the substituent compound formula (15) with three formulas (13) and the compound of formula (14) of using reacts the compound that is obtained, compound shown in the preferred use formula (25) is (in the formula (25), Y represent direct key or-C (=O)-, Ar represents can be 1～6 alkyl by carbon number, phenyl, naphthyl, halogen atom, carbon number is 1～6 alkoxy carbonyl, nitro, carboxyl, cyano group, carbon number is 1～6 alkoxy, hydroxyl, mercapto, carbon number is 1～6 alkyl sulfenyl or amino phenyl ring or the naphthalene nucleus that replaces).

As with the reaction that on nitrogen-atoms, has the substituent triazinetrione compound shown in the formula (13) in the compound of the formula (14) used, can list 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).Compound in this reaction Chinese style (16)～(21) can only use a kind, also can will be used in combination more than 2 kinds or 2 kinds.

Have the substituting group shown in the formula (3) as the substituent triazinetrione compound on the nitrogen-atoms as above-mentioned, can use compound with the structure shown in the formula (7).In the formula (7), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, R ₁The expression carbon number is 1～6 alkyl, phenyl or benzyl, R ₂Expression hydrogen atom, carbon number are 1～6 alkyl.As carbon number is 1～6 alkyl, for example is methyl, ethyl, n-pentyl, isopropyl, cyclohexyl etc.

The compound of formula (7), can be by making carbon dioxide and on nitrogen-atoms, having the substituent triazinetrione compound reaction shown in the formula (13), after making epoxide ring partly be transformed into dioxane pentanone (ジオキシラノ Application) ring, itself and amines formula (26) reaction are made.

Make epoxide ring partly be transformed into the reaction of dioxane pentanone (ジオキシラノ Application) ring, for example, can itself and carbon dioxide reaction be carried out by in the presence of lithium bromide.In addition, the reaction of dioxane pentanone (ジオキシラノ Application) ring and amines formula (26) for example, can in the dinethylformamide, be carried out 70 ℃ of reactions by at N in 48 hours.

In this reaction, when use has the triazinetrione compound of two or three substituent nitrogen-atoms with formula (13), after having its whole epoxide rings partly to be transformed into dioxane pentanone (ジオキシラノ Application) ring as can be known, the substituent situation of a conversion accepted way of doing sth (3), with the substituent situation of having only one of them or two epoxide ring part conversion accepted way of doing sth (3), and the triazinetrione compound that uses in the composition of formation antireflection film of the present invention is the compound that comprises its any situation.

As on nitrogen-atoms, having the substituent triazinetrione compound shown in the formula (13), the preferred substituent compound with three formulas (13), the compound of promptly above-mentioned formula (15) of using.Thereby, in the composition of formation antireflection film of the present invention, the preferred substituent compound that uses whole epoxide ring part conversion accepted way of doing sth (3) of substituent compound formula (15) with three formulas (13), promptly preferably use the compound shown in the formula (27) (in the formula (27), R ₁, R ₂Identical with above-mentioned definition).

As with the reaction that on nitrogen-atoms, has the substituent triazinetrione compound shown in the formula (13) in the compound of the formula (26) used, for example can list methylamine, ethamine, isopropylamine, n-butylamine, cyclohexylamine, aniline, benzylamine, dimethylamine, diethylamine, diisopropylamine, dibenzyl amine, diphenylamine etc.In this reaction, the compound of formula (26) can only use a kind, or, also can or be used in combination more than it 2 kinds.

Form in the composition at antireflection of the present invention, the compound shown in the formula (27) can use separately, also can or be used in combination more than it 2 kinds in addition.As the use level of such formula (27) compound, be more than or equal to 10% quality in all solids composition, for example be 30% quality～99% quality, for example be 50% quality～99% quality, and then for example be 60% quality～95% quality.

In the composition of the formation antireflection film of the present invention that contains the compound shown in the formula (27), the characteristic of the antireflection film that forms by this composition that forms antireflection film, particularly to the extinction characteristic of the irradiates light that in photoetching process, uses, attenuation coefficient, refractive index etc., be the characteristic of kind that also depends on the compound of the formula of using in this reaction (26).

In the composition of formation antireflection film of the present invention, as above-mentioned triazinetrione oligomer compounds or triazinetrione macromolecular compound, can use triazinetrione oligomer compounds, triazinetrione macromolecular compound with the structure shown in the formula (8) with structure that at least two triazinetrione ring structures connect by its nitrogen-atoms by the connection base shown in the formula (4).In the formula (8), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, 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.

As the triazinetrione oligomer compounds in the composition of formation antireflection film of the present invention, the molecular weight of triazinetrione macromolecular compound with the structure shown in the formula (8), there is no particular limitation, and as weight-average molecular weight, for example be 700～200000, for example 1000～50000.

Triazinetrione oligomer compounds, triazinetrione macromolecular compound with the structure shown in the formula (8) can have the aromatics shown in two or three triazinetrione compounds that have the substituent nitrogen-atoms shown in the above-mentioned formula (13) on nitrogen-atoms and the above-mentioned formula (14) and react and obtain by making.In this reaction, can only use the compound shown in a kind of above-mentioned formula (14), also can or be used in combination more than it in addition 2 kinds.

This reaction is preferably carried out with the solution state of the organic solvent that is dissolved in benzene,toluene,xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-Methyl pyrrolidone etc.In addition, also can use the quaternary ammonium salt of benzyltriethylammoinium chloride, tetrabutylammonium chloride, tetraethylammonium bromide etc. as this catalyst for reaction.The temperature of reaction of this reaction, reaction time depend on the compound, concentration of use etc., and the reaction time can suitably be selected in 0.1～100 hour scope, and temperature of reaction can suitably be selected in 20 ℃～200 ℃ scope.When using catalyzer, can be to use in the scope of 0.001～50% quality at all-mass with respect to the compound that uses.

In this reaction, can use separately to have two or three have the substituent nitrogen-atoms shown in the above-mentioned formula (13) on nitrogen-atoms triazinetrione compound, also they can be used in combination in addition.The preferred substituent compound that uses with three formulas (13), that is, and the compound shown in the above-mentioned formula (15).

In this reaction, following two kinds of situations are arranged as can be known, that is, have the whole substituting groups of triazinetrione compound of two or three substituent nitrogen-atoms and the compound reaction of formula (14), participate in the situation of formation of the connection base of above-mentioned formula (4) with formula (13); Participate in the formation that is connected base of (4), the situation of the substituent formation of substituting group unreacted of remaining formula (13) or participatory (2) with the substituting group of one or two formula (13).In the triazinetrione oligomer compounds that obtains by this reaction, triazinetrione macromolecular compound, following two kinds of situations are arranged as can be known, promptly, become the formation of connection base of the substituting group participatory (4) of one or two formula (13) in its triazinetrione compound of making raw material, promptly participate in the formation of oligomer structure, macromolecular structure, the situation of the substituent formation of substituting group unreacted of remaining formula (13) or participatory (2); All formation of the connection base of the substituting group participatory (4) of the formula (13) of (that is, two or three) promptly participates in the situation of the formation of oligomer structure, macromolecular structure.

In the manufacturing of the triazinetrione oligomer compounds of utilizing this reaction to carry out and triazinetrione macromolecular compound, the preferred compound that uses as the above-mentioned formula (15) of substituent compound with three formulas (13), especially preferably use formula (28) compound (in the formula, A ₄Expression hydrogen atom or methyl).

Compound as the formula of using in the manufacturing of the triazinetrione oligomer compounds with structure shown in the formula (8), triazinetrione macromolecular compound (14) can list the compound with naphthalene nucleus shown in above-mentioned formula (16)～(21), have the compound of phenyl ring.These compounds can only use a kind, also can or be used in combination more than it 2 kinds in addition.

Antireflection film composition of the present invention is, contains the antireflection film composition of utilization has benzene compound shown in substituent triazinetrione compound shown in the formula (13) and the formula (14) or naphthalene compound on nitrogen-atoms the triazinetrione compound that reaction obtained, triazinetrione oligomer compounds, triazinetrione macromolecular compound.In antireflection film composition of the present invention, also comprise any of following composition: only contain such triazinetrione compound compositions, the composition that only contains the triazinetrione oligomer compounds, the composition that only contains the triazinetrione macromolecular compound, in addition, also comprise any of following composition: the composition that comprises the potpourri of such triazinetrione compound and triazinetrione oligomer compounds, the composition that comprises the potpourri of such triazinetrione compound and triazinetrione macromolecular compound, the composition that comprises the potpourri of such triazinetrione oligomer compounds and triazinetrione macromolecular compound, comprise such triazinetrione compound, the composition of the potpourri of triazinetrione oligomer compounds and triazinetrione macromolecular compound.

Containing in utilization has the triazinetrione compound that reaction obtained of compound of substituent triazinetrione compound shown in the formula (13) and formula (14) or triazinetrione oligomer compounds or triazinetrione macromolecular compound on nitrogen-atoms the composition of formation antireflection film of the present invention, the characteristic of the antireflection film that forms by said composition, particularly to the extinction characteristic of the irradiates light that in photoetching process, uses, attenuation coefficient, refractive index etc., be the characteristic of kind that depends on the compound of the formula of using in this reaction (14) greatly.In addition, the kind of the compound of the formula of use (14), etched to remove the needed time of operation also influential to utilizing of the antireflection film that formed by the composition that forms antireflection film of the present invention.Particularly, phenyl ring in formula (14) compound, the substituent kind and the quantity of naphthalene nucleus, etched to remove the needed time of operation influential to utilizing of antireflection film, contain the heteroatomic substituting group of halogen atom, nitrogen-atoms, oxygen atom, sulphur atom etc. or increase this substituent quantity by introducing, can shorten and utilize removing the needed time of operation that etching carries out.

When the technology of the light that antireflection film composition of the present invention has been used to use wavelength 248nm (KrF excimer laser),, preferably use the compound shown in formula (16)～(18) with naphthalene nucleus as the compound of formula (14).In addition, when the technology of the light that is used to have used wavelength 193nm (ArF excimer laser) and wavelength 157nm (F2 excimer laser), preferably use the compound shown in formula (19)～(21) with phenyl ring.

As such compound with naphthalene nucleus, for example can list, 3-hydroxyl naphthalene-2-formic acid, naphthalene-2,6-dioctyl phthalate, naphthalene-2,3-dioctyl phthalate, 1,6-two bromo-2 hydroxy naphthalene-3-formic acid, 6-hydroxyl naphthalene-2-formic acid, 3,7-dihydroxy naphthlene-2-formic acid, 4-hydroxyl-1-phenyl-naphthalene-2-formic acid, 6-hydroxyl naphthalene-2-formic acid, 4-bromonaphthalene-1,8-dioctyl phthalate, 2 hydroxy naphthalene-1-formic acid, 4-bromonaphthalene-1,4-dioctyl phthalate, 1,5-dihydroxy naphthlene, 2,6-two bromo-1,5-dihydroxy naphthlene, 1,7-dihydroxy naphthlene, 6-ethoxy-2,3-dihydroxy naphthlene etc.

As such compound with phenyl ring, for example can list, the 3-hydroxybenzoic acid, 3, the 5-dihydroxy-benzoic acid, 2-amino-3-hydroxy formic acid, 2,5-two chloro-3-hydroxyl-6-methoxy benzoic acids, 2,4,6-three iodo-3-hydroxybenzoic acids, 2,4,6-three bromo-3-hydroxybenzoic acids, 2-bromo-4,6-dimethyl-3-hydroxybenzoic acid, 2-fluoro-5-hydroxybenzoic acid, 3-methoxyl-4-hydroxybenzoic acid, 3,5-two bromo-4-hydroxybenzoic acids, 2,4-dihydroxy-5-bromobenzoic acid, 3-iodo-5-nitro-4-hydroxybenzoic acid, 2 hydroxybenzoic acid, 4-chloro-2 hydroxybenzoic acid, 3,5-two iodo-2 hydroxybenzoic acids, 3-methoxyl-2 hydroxybenzoic acid, 2-hydroxyl-6-isopropyl-3-methyl benzoic acid, 4-amino-3,5-two iodo-2 hydroxybenzoic acids, 4,5-two chloro-benzene-1, the 3-dioctyl phthalate, 5-amino-2,4,6-three iodo-m-phthalic acids, benzene-1, the 4-dioctyl phthalate, 2,3,5,6-tetrabromo-benzene-1, the 4-dioctyl phthalate, 4,5-two chloro-o-phthalic acids, 5-methoxyl-3-methyl-phthalic acid, 3,4,5,6-tetrabromophthalate etc.

In the composition of formation antireflection film of the present invention, as above-mentioned triazinetrione oligomer compounds or triazinetrione macromolecular compound, can use triazinetrione oligomer compounds, triazinetrione macromolecular compound with the structure shown in the formula (9) with structure that at least two triazinetrione rings connect by the connection base shown in the formula (5) on its nitrogen-atoms.In the formula (9), A ₁, A ₂And A ₃Represent hydrogen atom, methyl or ethyl respectively, 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, R ₂Expression hydrogen atom, carbon number are 1～6 alkyl, phenyl or benzyl.

As the triazinetrione oligomer compounds in the composition of formation antireflection film of the present invention, the molecular weight of triazinetrione macromolecular compound with the structure shown in the formula (9), there is no particular limitation, but as weight-average molecular weight, for example being 700～200000, for example is 1000～50000.

Triazinetrione oligomer compounds, triazinetrione macromolecular compound with the structure shown in the formula (9), can be by making carbon dioxide and on nitrogen-atoms, having the substituent triazinetrione compound reaction shown in the formula (13), after making epoxide ring partly be transformed into dioxane pentanone (ジオキシラノ Application) ring, itself and amines formula (29) reaction are made.

The reaction of dioxane pentanone (ジオキシラノ Application) ring and amines formula (29) for example, can in the dinethylformamide solvent, be carried out 70 ℃ of reactions by at N in 48 hours.In this reaction, the compound shown in the formula (29) can only use a kind of, in addition, also can or be used in combination more than it two kinds.

In this reaction, can use separately to have two or three have the substituent nitrogen-atoms shown in the formula (13) on nitrogen-atoms triazinetrione compound, in addition, also they can be used in combination.The preferred substituent compound that uses with three formulas (13), that is, and the compound shown in the above-mentioned formula (15).

In this reaction, following two kinds of situations are arranged as can be known, promptly, the whole epoxide rings part of triazinetrione compound with two or three substituent nitrogen-atoms with formula (13) is after being transformed into dioxane pentanone (ジオキシラノ Application) ring, with the reaction of the compound of formula (29), participate in the situation of formation of the connection base of above-mentioned formula (5); With the formation that is connected base of the epoxide ring subparticipation (5) of one or two formula (13), the substituting group (R of substituting group unreacted of remaining formula (13) or participatory (3) ₂Be hydrogen atom) the situation of formation.In the triazinetrione oligomer compounds that obtains by this reaction, triazinetrione macromolecular compound, following two kinds of situations are arranged as can be known, promptly, one or two formula (13) the substituting group participatory (5) that becomes in its triaizine compounds of making raw material connects basic formation, promptly participate in the formation of oligomer structure, macromolecular structure, the situation of remaining formula (13) substituting group unreacted or the substituent formation of participatory (3); Or all (that is, two or three) formula (13) substituting group participatory (5) connects the formation of base, promptly participates in the situation of the formation of oligomer structure, macromolecular structure.

In the manufacturing of the triazinetrione oligomer compounds of utilizing this reaction and triazinetrione macromolecular compound, the preferred use as compound with above-mentioned formula (15) of the substituent compound of three formulas (13), the preferred especially compound that uses above-mentioned formula (28).

Compound as the formula of in the manufacturing of the triazinetrione oligomer compounds with structure shown in the formula (9), triazinetrione macromolecular compound, using (29), for example can list, ethylenediamine, propane diamine, phenylenediamine, 2-hydroxyl-1,3-propane diamine, 1,4-cyclohexanediamine, xylylene diamine, 2,6-dichloro-benzenes diamines, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene etc.These compounds can only use a kind, also can or be used in combination more than it two kinds.

In the composition of the formation antireflection film of the present invention of the triazinetrione oligomer compounds that contains the structure shown in the formula (9), triazinetrione macromolecular compound, the characteristic of the antireflection film that forms by said composition,, be the characteristic that depends on the kind of formula (29) compound that uses in this reaction particularly to the extinction characteristic of the irradiates light that in photoetching process, uses, attenuation coefficient, refractive index etc.In addition, the kind of the compound of the formula of use (29), etched to remove the needed time of operation also influential to utilizing of the antireflection film that formed by the composition that forms antireflection film of the present invention.

When the technology of the light that antireflection film composition of the present invention has been used to use wavelength 248nm (KrF excimer laser), as the compound of formula (29), preferably use 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, the compound with naphthalene nucleus of 3--diaminonaphthalene etc.In addition, when the technology of the light that is used to have used wavelength 193nm (ArF excimer laser) and wavelength 157nm (F2 excimer laser), preferred phenylenediamine, the benzene dimethylamine, 2 of using, 6-dichloro-benzenes diamines, 3,5-two bromo-1,2-phenylenediamine, 3,4,5, the 6-tetraiodo-1, the compound with phenyl ring of 2-phenylenediamine etc.

Contain in the composition as formation antireflection film of the present invention, has the substituting group shown in formula (2) or the formula (3) as the substituent triazinetrione compound on the nitrogen-atoms, have the triazinetrione oligomer compounds of the structure that at least two triazinetrione rings connect by the connection base shown in formula (4) or the formula (5) or triazinetrione macromolecular compound on its nitrogen-atoms, the base that is connected of the substituting group of formula (2), formula (3) and formula (4), formula (5) can be listed below.

For example, as the substituting group of formula (2), be the substituting group of formula (30)～(37).

For example, as the substituting group of formula (3), be the substituting group of formula (38)～(43).

In addition, as the connection base of formula (4), for example be the connection base of formula (44)～(52).

In addition, as the connection base of formula (5), for example be the connection base of formula (54)～(55).

In the composition of formation antireflection film of the present invention, as having the hydroxy alkyl structure, can also list the resultant of reaction of the compound shown in compound shown in the formula (10) and formula (11) or the formula (12) as the substituent triazinetrione compound on the nitrogen-atoms.R 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.As carbon number is 1～6 alkyl, for example is methyl, ethyl, n-pentyl, isopropyl, cyclohexyl etc.As carbon number is 3～6 alkenyl, for example is allyl, 2-butenyl group, 3-butenyl group, 2-pentenyl etc.

By making the compound of formula (10) and formula (11), for example, in the solvent of cyclohexanone, propylene glycol monomethyl ether etc., be catalyzer with the benzyl triethyl ammonium bromide, under reflux, react, can obtain the compound that forms by the structural unit shown in the formula (56) as resultant of reaction.

In addition, R in formula (10) ₃Be 2, during the 3-glycidyl, its three epoxide ring parts can be reacted with the compound of formula (11), can obtain to have the compound of the structural unit shown in the formula (57).

The quantity of the structural unit of formula that contains in the resultant of reaction (56) and formula (57) changes with the change of reaction conditions.As the resultant of reaction of the composition that is used for formation antireflection film of the present invention, the preferred structural unit that contains 1～10000 formula (56) that uses, molecular weight is counted 400～1000000 oligomer compounds, macromolecular compound with weight-average molecular weight.In addition, the preferred structural unit that contains 1～10000 formula (57) that uses, molecular weight is counted 400～1000000 oligomer compounds, macromolecular compound with weight-average molecular weight.

By making the compound of formula (10) and formula (12), for example, in the solvent of cyclohexanone, propylene glycol monomethyl ether etc., be catalyzer with the benzyl triethyl ammonium bromide, under reflux, react, can obtain resultant of reaction.In formula (12), R ₆During for the alkyl of carbon number 1～6, phenyl or benzyl, the compound that the epoxide ring that can obtain carboxyl of formula (12) and formula (10) as resultant of reaction has reacted.R in formula (12) ₆For-(CH ₂) _nDuring COOH, two carboxyl respectively with the epoxide ring reaction of the compound shown in the other formula (10), can obtain the compound that forms by the structural unit shown in the formula (58) as resultant of reaction.

In addition, R in formula (10) ₃Be 2, during the 3-glycidyl, its three epoxide rings part all can with the carboxyl reaction of formula (12), can obtain to have the compound of the structural unit shown in the formula (59).

The quantity of the structural unit of formula that contains in the resultant of reaction (58) and formula (59) changes with the change of reaction conditions.As the resultant of reaction that in the composition of formation antireflection film of the present invention, uses, the preferred structural unit that contains 1～10000 formula (58) that uses, molecular weight is counted 400～1000000 oligomer compounds, macromolecular compound with weight-average molecular weight.In addition, the preferred structural unit that contains 1～10000 formula (59) that uses, molecular weight is 400～1000000 oligomer compounds, macromolecular compound with weight-average molecular weight.

In the composition of formation antireflection film of the present invention, also the resultant of reaction that contains the structural unit of formula (56) can be used in combination with the resultant of reaction that contains the structural unit of formula (58).

Compound as the formula of in the manufacturing of resultant of reaction, using (10), for example can list monoene propyl group diglycidyl cyamelide, monomethyl diglycidyl cyamelide, single ethyl diglycidyl cyamelide, monobutyl diglycidyl cyamelide, single phenyl diglycidyl cyamelide, monobenzyl diglycidyl cyamelide.

As the compound of formula (11), for example can list monoene propyl group cyamelide, monomethyl cyamelide, single ethyl cyamelide, monobutyl cyamelide, single phenyl cyamelide, monobenzyl cyamelide.

In addition, compound as formula (12), for example can list dimethyl mono carboxylic ethyl cyamelide, diethyl mono carboxylic ethyl cyamelide, diallyl carboxy ethyl cyamelide, dibutyl mono carboxylic ethyl cyamelide, diphenyl mono carboxylic ethyl cyamelide, dibenzyl mono carboxylic ethyl cyamelide.

The composition of formation antireflection film of the present invention, for prevent with its on the mixing of photoresist of coating, preferably after coating by heating and crosslinked, the composition of formation antireflection film of the present invention can also contain the crosslinking chemical composition.As such crosslinking chemical, can list and have substituent melamine compounds of being cross-linked to form of so-called methylol, methoxy or substitute urea compound, have the macromolecular compound of epoxy radicals etc.Be cross-linked to form substituent crosslinking chemical as having 2 at least, the compound of methoxy glycoluril or methoxy melamine etc. is arranged, be preferably tetramethoxymethylglycoluril or own oxygen methyl melamine.In addition, can also list the compound of tetramethoxy methyl urea, four butoxymethyl ureas etc.The addition of crosslinking chemical, wait according to the film shape of the solution viscosity of the basal substrate of the coating solvent that uses, use, requirement, requirement and to change, and in whole compositions, be 0.001～20% quality, be preferably 0.01～15% quality, more preferably 0.05～10% quality.Cross-linking reaction takes place by self condensation in these crosslinking chemicals sometimes, but also can with the composition of formation antireflection film of the present invention in contain have the hydroxy alkyl structure as the substituent triazinetrione compound on the nitrogen-atoms, has the hydroxy alkyl structure as the substituent triazinetrione oligomer compounds on the nitrogen-atoms or have the be cross-linked to form substituting group of hydroxy alkyl structure as the substituent triazinetrione macromolecular compound on the nitrogen-atoms, for example, above-mentioned formula (1), formula (2), formula (3), formula (4), formula (5), formula (56), formula (57), formula (58), hydroxyl generation cross-linking reaction in the formula (59).

As the catalyzer that is used to promote above-mentioned cross-linking reaction in the present invention, the acid compound and/or 2 that can cooperate p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid pyridiniujm, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid etc., 4,4, the hot acid propellant of 6-tetrabromo cyclohexadiene ketone, benzoin tosylate (benzointosylate), 2-nitrobenzyl tosylate (2-nitrobenzyltosylate) etc.Use level for example is 0.02～10% quality in all solids composition, or for example is 0.04～5% quality.

In the composition of formation antireflection film of the present invention, can also add and have at least one that be selected from hydroxyl, carboxyl, amino, the mercapto and be cross-linked to form substituent resin.By adding such resin, can regulate the characteristic of the refractive index, attenuation coefficient, etching speed etc. of the antireflection film that forms by the composition that forms antireflection film of the present invention.As such resin, can list and contain the resin as a structural unit such as 2-Hydroxy ethyl acrylate, acrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, vinyl alcohol, 2-hydroxyethyl vinethene, acrylic acid, methacrylic acid.As the weight-average molecular weight of such resin, can be 500～1000000, be preferably 500～500000, be preferably 100～100000 in addition.The content of the such resin in the composition of formation antireflection film of the present invention is the ratio smaller or equal to 20% quality in all solids composition, is preferably the ratio smaller or equal to 15% quality.

As such resin, for example can list, polymethacrylate-2-hydroxy-ethyl ester, polyvinyl alcohol (PVA), polyacrylic acid, the multipolymer of acrylic acid-2-hydroxy propyl ester and methyl methacrylate, the multipolymer of acrylic acid-2-hydroxy propyl ester and isopropyl methacrylate, methacrylic acid 2-hydroxypropyl acrylate and methacrylic acid-2,2, the multipolymer of 2-trichloro ethyl ester, methacrylic acid-2-hydroxy propyl ester and methacrylic acid-2,2, the multipolymer of 2-trifluoro ethyl ester, the multipolymer of methacrylic acid-2-hydroxy propyl ester and methacrylic acid-2-chloroethene ester, the multipolymer of methacrylic acid-2-hydroxy propyl ester and cyclohexyl methacrylate, the multipolymer of methacrylic acid-2-hydroxy propyl ester and n octyl methacrylate, the multipolymer of methacrylic acid-2-hydroxy propyl ester and vinyl alcohol, methacrylic acid-2-hydroxy propyl ester and acrylic acid multipolymer, the multipolymer of methacrylic acid-2-hydroxy propyl ester and maleimide, the multipolymer of methacrylic acid-2-hydroxy propyl ester and vinyl cyanide, the multipolymer of vinyl alcohol and methyl methacrylate, the multipolymer of vinyl alcohol and maleimide, the multipolymer of vinyl alcohol and methyl methacrylate, the multipolymer of 2-hydroxyethyl vinethene and methacrylic acid ethyl ester, the multipolymer of 2-hydroxyethyl vinethene and methacrylic acid-2-hydroxy propyl ester, the multipolymer of methacrylic acid and Jia Jibingxisuanyizhi, the multipolymer of methacrylic acid and maleimide etc.

The composition of formation antireflection film of the present invention in order to make its acidity with the photoresist that is overlayed on the upper strata in photoetching process consistent, can add light acid propellant.As preferred light acid propellant, for example can list, the salt acid-producing agent class of two (4-tert-butyl-phenyl) trifluoromethanesulfonic acid salt compounded of iodine, triphenyl trifluoromethanesulfonic acid sulfonium salt etc., the halide-containing class light acid propellant class of two (the trichloromethyl)-s-triazines of phenyl etc., the acids light acid propellant class of benzoin tosylate (benzointosylate), N-hydroxy-succinamide base triflate etc. etc.The addition of above-mentioned light acid propellant is 0.02～3% quality in all solids composition, is preferably 0.04～2% quality.

In the composition of formation antireflection film of the present invention, can also add light-absorbing compound, light absorptive resin.By adding light-absorbing compound, light absorptive resin, can regulate the characteristic of the refractive index, attenuation coefficient, etching speed etc. of the antireflection film that forms by the composition that forms antireflection film of the present invention.As such light-absorbing compound, light absorptive resin, so long as the light in the sensitometric characteristic wavelength field that is arranged on the photographic composition in the photoresist layer on the antireflection film is had very high absorption energy, can prevent by from the reflection of substrate and the diffuse reflection that the injustice of standing wave that generates and substrate surface causes just can use.In addition, as the weight-average molecular weight of the light absorptive resin that uses, be 500～1000000, be preferably 500～500000 or 1000～100000.

These light-absorbing compounds, light absorptive resin can only use a kind, also can or be used in combination more than it 2 kinds.The use level of the light-absorbing compound in the composition of formation antireflection film of the present invention, light absorptive resin, be more than or equal to 0.01% quality in all solids composition, being 1% quality～90% quality, for example is 1% quality～50% quality, for example is 5% quality～40% quality.

As light-absorbing compound, for example can use phenyl compound, benzophenone cpd, benzotriazole cpd, azo-compound, naphthalene compound, anthracene compound, anthraquinone compounds, triaizine compounds, triazinetrione compound, quinoline compound etc.Preferred phenyl compound, naphthalene compound, anthracene compound, triaizine compounds, the triazinetrione compound of using.

Preferred use has the phenyl compound of hydroxyl, amino or a carboxyl at least, has the naphthalene compound of hydroxyl, amino or a carboxyl at least, has the anthracene compound of hydroxyl, amino or a carboxyl at least.

As the phenyl compound that has hydroxyl, amino or a carboxyl at least, for example can list, phenol, bromophenol, 4,4 '-diphenylsulfone phenol, tert-butyl phenol, xenol, benzoic acid, salicylic acid, hydroxyl m-phthalic acid, phenylacetic acid, aniline, benzene methanamine, phenmethylol, styron, phenylalanine, phenoxypropanol etc.

As the naphthalene compound that has hydroxyl, amino or a carboxyl at least, for example can list, 1-naphthoic acid, 2-naphthoic acid, 1-naphthols, beta naphthal, 1-amino naphthalenes, methyl, 1-hydroxyl-2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2 hydroxy naphthalene, 2,6-naphthalenedicarboxylic acid etc.

As the anthracene compound that has hydroxyl, amino or a carboxyl at least, for example can list 9-anthroic acid, 9-hydroxymethyl anthracene, 1-amino anthracene etc.

As the light absorptive resin, for example, can use in its structure, have phenyl ring, the resin of aromatic heterocycle structure that aromatic ring structure, pyridine ring, quinoline ring, thiphene ring, thiazole ring, triazine ring, oxazole ring that naphthalene nucleus, anthracene nucleus are such are such.

As such light absorptive resin, can use in its constitutional repeating unit, to have at least one the resin of aromatic ring structure that is selected from phenyl ring, naphthalene nucleus and the anthracene nucleus.

As resin, can list phenolic novolac, halogenation phenolic novolac, polystyrene, polycarboxylated styrene etc. with phenyl ring.In addition, can also list and contain the resin as structural unit such as acrylic acid benzyl ester, methacrylic acid benzyl ester, styrene, hydroxy styrenes.As such resin, can list multipolymer, methacrylic acid benzyl ester and methacrylic acid-2-hydroxy propyl ester and terpolymer, styrene and the methacrylic acid-2-hydroxy methacrylate of Jia Jibingxisuanyizhi and the terpolymer of methyl methacrylate etc. of multipolymer, hydroxy styrenes and Jia Jibingxisuanyizhi of multipolymer, styrene and the methacrylic acid-2-hydroxy methacrylate of methacrylic acid benzyl ester and methacrylic acid-2-hydroxy propyl ester.

And then, as resin with phenyl ring, can also list in No. 6323310, the United States Patent (USP) disclosed, the resin that produces by melamine compound (trade name サイメ Le 303) and benzoguanamine compound (trade name サイメ Le 1123).

As resin with naphthalene nucleus, anthracene nucleus, for example can list, have the resin of structural unit shown below ((a)～(g)).

In the composition of formation antireflection film of the present invention, except above-mentioned, can also further add rheology control agent, bonding assistant, surfactant etc. as required.

Rheology control agent mainly is the flowability for the composition that improves the formation antireflection film, and in roasting procedure, raising is added to the fillibility of the composition of the formation antireflection film of inside, hole especially.As concrete example, can list, repefral, diethyl phthalate, diisobutyl phthalate, dihexylphthalate, the phthalic acid derivatives of butyl phthalate isodecyl ester etc., Di-n-butyl Adipate, diisobutyl adipate, diisooctyl adipate, the hexane diacid derivant of octyl adipate ester in the last of the ten Heavenly stems etc., n-butyl maleate, diethyl maleate, the maleic acid derivatives of dinonyl maleate etc., methyl oleate, butyl oleate, the oleic acid derivant of tetrahydrofurfuryl oleate etc., or n-butyl stearate, the stearic acic derivative of tristerin etc.These rheology control agents in the whole compositions of photoetching with the composition that forms antireflection film, cooperate with the ratio less than 30% quality usually.

The bonding assistant mainly is the adhesiveness for the composition that improves substrate or photoresist and formation antireflection film, photoresist is not peeled off added.As concrete example, can list, trimethyl chlorosilane, the dimethyl vinyl chlorosilane, methyldiphenyl base chlorosilane, chlorosilane classes such as CMDMCS chloromethyl dimethyl chlorosilane, the trimethyl methoxy silane, dimethyldiethoxysilane, methyl dimethoxysilane, dimethyl vinyl Ethoxysilane, dimethoxydiphenylsilane, the alkoxyl silicone alkanes of phenyl triethoxysilane etc., hexamethyldisilazane, N, N '-two (trimethyl silyl) urea, dimethyl trimethyl silyl amine, the silazane class of trimethyl-silyl-imidazole etc., vinyl trichlorosilane, γ-r-chloropropyl trimethoxyl silane, γ-An Jibingjisanyiyangjiguiwan, the silanes of γ-glycidoxypropyltrime,hoxysilane etc., benzotriazole, benzimidazole, indazole, imidazoles, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, the 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, the heterogeneous ring compound of mercaptopyrimidine etc., or 1, the 1-dimethyl urea, 1, the urea or the thiourea compound of 3-dimethyl urea etc.These assistants that bond in the whole compositions of photoetching with the composition that forms antireflection film, cooperate with the ratio less than 5% quality usually, preferably cooperate with the ratio less than 2% quality.

In the composition of formation antireflection film of the present invention, in order not produce pin hole or striped, and then improve coating to uneven surface, can the matching surface activating agent.As surfactant, for example can list, polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, the polyoxyethylene cetyl ether, the polyoxyethylene alkyl ether class of polyoxyethylene oleyl ether etc., polyoxyethylene octyl phenol ether, the polyoxyethylene alkylaryl ether class of polyoxyethylene nonylphenyl ether etc., the polyoxyethylene polyoxypropylene block copolymer class, sorbitan monolaurate, sorbitan-monopalmityl ester, the anhydrosorbitol monostearate, dehydrating sorbitol monooleate, the anhydrosorbitol trioleate, the sorbitan fatty ester class of anhydrosorbitol tristearate etc., the polyoxyethylene sorbitan monolaurate, the polyoxyethylene sorbitan monopalmitate, the polyoxyethylene sorbitan monostearate, the polyoxyethylene sorbitan trioleate, the non-ionic surfactant of the polyoxyethylene sorbitan fatty acid ester of polyoxyethylene sorbitan tristearate etc. etc., エ Off ト Star プ EF301, EF303, EF352 ((strain) ト one ケ system プロダ Network Star system), マガ Off ア Star Network F171, F173 (big Japanese イ Application キ (strain) system), Off ロラ one De FC430, FC431 (Sumitomo スリ one エ system (strain) system), アサヒガ one De AG710, サ one Off ロ Application S-382, SC-101, SC-102, SC-103, SC-104, SC-105, the fluorine class surfactant of SC-106 (Asahi Glass (strain) system) etc., organic siloxane polymer K P341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) etc.The use level of these surfactants in the whole compositions of photoetching of the present invention with the composition that forms antireflection film, is generally smaller or equal to 0.2% quality, is preferably smaller or equal to 0.1% quality.These surfactants can add separately, also can be with 2 kinds or combination interpolation more than it.

In the present invention, solvent as the above-mentioned polymkeric substance of dissolving can use glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, cyclohexanone, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxy-propionic acid methyl esters, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate etc.These organic solvents can use separately or with 2 kinds or be used in combination more than it.

And then, can mix the high boiling solvent that uses propylene glycol monobutyl ether, propylene glycol monobutyl ether acetic acid esters etc.In these solvents, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, butyl lactate and cyclohexanone are preferred from improving the levelability aspect.

As the photoresist on the upper strata of coating antireflection film of the present invention, can use any one of minus, eurymeric.Have and contain light acid propellant and have the chemical amplification type anti-corrosion agent of decomposing the bonding agent of the group that improves alkali dissolution speed by acid, the chemical amplification type anti-corrosion agent that contains alkali solubility bonding agent and light acid propellant and decompose the low molecular compound of the alkali dissolution speed that improves resist by acid, contain light acid propellant and have the chemical amplification type anti-corrosion agent etc. of decomposing the bonding agent of the group that improves alkali dissolution speed and decomposing the low molecular compound of the alkali dissolution speed that improves resist by acid by acid, for example can list シプレ one society's system, trade name APEX-E.In addition, also as listing Proc.SPIE, Vol.3999,330-334 (2000), Proc.SPIE, Vol.3999,357-364 (2000), Proc.SPIE, the contain fluorine atoms polymer class photoresist of record among the Vol.3999,365-374 (2000).

Use the developer solution of photoetching of the present invention as having with the positive light anti-etching agent of the formed antireflection film of composition that forms antireflection film, can use NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, the inorganic base of ammoniacal liquor etc., ethamine, the primary amine class of n-propylamine etc., diethylamine, the secondary amine class of di-n-butylamine etc., triethylamine, the tertiary amines of methyl-diethyl-amine etc., dimethylethanolamine, the alcamines of triethanolamine etc., tetramethylammonium hydroxide, tetraethylammonium hydroxide, the quaternary ammonium salt of choline etc., the pyrroles, the aqueous solution of the bases of the cyclic amine of piperidines etc. etc.And then, also can in above-mentioned bases aqueous solution, add the alcohols of isopropyl alcohol etc. in right amount, the surfactant of nonionic class uses.Wherein preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.

Below, forming method to photoresist figure of the present invention describes, employed substrate (for example in the manufacturing of accurate integrated circuit component, silicon/silicon dioxide is substrate coated, silicon nitride substrate, glass substrate, ito substrate etc.) on utilize the suitable coating process of spin coating, coating etc. to be coated with the composition that forms antireflection film after, burn till (baking) and it solidified make antireflection film.Here, as the thickness of antireflection film, for example be 0.01～3.0 μ m, or for example be 0.03～1.0 μ m.In addition, after coating, as firing condition, for example for to burn till 0.5～120 minute at 80～250 ℃, or for example for to burn till 0.5～10 minute at 150～250 ℃.Then, by painting photoresist, the mask that sees through regulation exposes, and development, flushing, drying can obtain good photoresist figure.Back heating (PEB:Post ExposureBake) as required can also expose.Then, that part of antireflection film of having removed photoresist by above-mentioned operation development is removed by dry ecthing, can on substrate, be formed desirable figure.

By contain of the present invention 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 antireflection film that the hydroxy alkyl structure forms as the composition that forms antireflection film of the substituent triazinetrione macromolecular compound on the nitrogen-atoms, having effectively, absorbing wavelength is that 248nm, wavelength are that 193nm or wavelength are the character of the irradiates light of 157nm.Therefore, to the catoptrical effect height that prevents from substrate reflection, its result can form the photoresist figure on upper strata well.In addition, by contain of the present invention 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 antireflection film that the hydroxy alkyl structure is made as the composition that forms antireflection film of the substituent triazinetrione macromolecular compound on the nitrogen-atoms, owing to contain the structure of comprising of so-called triazinetrione ring of a large amount of heteroatomss (nitrogen-atoms, oxygen atom), so compare with photoresist, it has very big dry etching rate.

In addition, the structure of the Ar part that contains in the connection base of the structure of the M part that contains in the compound by selecting type (1) or the substituting group of formula (2) expression and formula (4) expression, promptly, select the ring structure of phenyl ring, naphthalene nucleus or anthracene nucleus and substituent kind, the quantity on these rings, can also regulate extinction characteristic to the antireflection film of employed irradiates light, attenuation coefficient, refractive index etc.

As the attenuation coefficient k value of the antireflection film that forms by the composition that forms antireflection film of the present invention, be the light of 248nm to wavelength, be 0.40～0.65, or be 0.40～0.60, or be 0.45～0.65.In addition, be the light of 193nm to wavelength, be 0.20～0.60, or be 0.25～0.60.In addition, be the light of 157nm to wavelength, be 0.20～0.50, or be 0.30～0.45, or be 0.30～0.40.

And then the antireflection film that is formed by the composition that forms antireflection film of the present invention by different process conditions, can be used as the film with following function and uses, and, prevents catoptrical function that is; With so have the interaction that prevents substrate and photoresist, prevent that the material that uses or the material that generates are to the bad influence of substrate or prevent when the exposure or the functions such as bad influence to photoresist of the material that generates during heating in photoresist when photoresist exposes from substrate.

Below, further specifically describe the present invention by embodiment, comparative example, but the present invention is not limited only to this.

Synthesis example 1

Make 5.0g three-(2, the 3-glycidyl)-after isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 4.8g 6-hydroxyl-2-naphthoic acid and 0.02g benzyltriethylammoinium chloride are dissolved in the 39g propylene glycol monomethyl ether, make it 130 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 3400 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, in the oligomer compounds that obtains by this synthesis example, contain triazinetrione compound with substituting group formula (35) with by the oligomer compounds that is connected basic formula (52) connection triazinetrione ring.

Synthesis example 2

Make 4.0g three-(2, the 3-glycidyl)-after isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 6.1g6-hydroxyl-2-naphthoic acid and 0.02g benzyltriethylammoinium chloride are dissolved in the 42g propylene glycol monomethyl ether, make it 130 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 1700 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 3

Make 4.0g three-(2, the 3-glycidyl)-after isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 7.2g 6-hydroxyl-2-naphthoic acid and 0.02g benzyltriethylammoinium chloride are dissolved in the 45g propylene glycol monomethyl ether, make it 130 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 1200 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 4

Make 1.7g three-(2, the 3-glycidyl)-after isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 3.4g 6-hydroxyl-2-naphthoic acid and 0.09g benzyltriethylammoinium chloride are dissolved in the 20g propylene glycol monomethyl ether, make it 130 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 1200 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 5

After making 21g glycidyl methacrylate and 39g methacrylic acid-2-hydroxy propyl ester be dissolved in the 242g propylene glycol monomethyl ether, it is warming up to 70 ℃.Then, with reactant liquor in 70 ℃ of insulations, add the 0.6g azobis isobutyronitrile, 70 ℃ of reactions 24 hours, obtain the solution of the copolymerization macromolecular compound of glycidyl methacrylate and methacrylic acid-2-hydroxy propyl ester.The macromolecular compound that obtains is carried out gpc analysis, and the result is 50000 by the weight-average molecular weight of polystyrene standard calibration.

Have in the solution of this copolymerization macromolecular compound of 20g to 100g, add 10g 9-anthroic acid, 0.3g benzyltriethylammoinium chloride and 41g propylene glycol monomethyl ether, at 130 ℃ of reactions 24 hours, the solution of the macromolecular compound of acquisition formula (60).N, m represent the mol ratio of this structural unit monomer, n+m=1 in the formula (60).

Synthesis example 6

Make 0.70g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 2.44g 2,4, after 6-three bromo-3-hydroxybenzoic acids and 0.04g benzyltriethylammoinium chloride are dissolved in the 12.72g propylene glycol monomethyl ether, behind nitrogen replacement, make it 125 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 1300 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, in the oligomer compounds that obtains by this synthesis example, contain triazinetrione compound with substituting group formula (30) with by the oligomer compounds that is connected basic formula (45) connection triazinetrione ring.

Synthesis example 7

Make 2.0g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 6.70g 3, after 5-two iodo-2 hydroxybenzoic acids and 0.115g benzyltriethylammoinium chloride are dissolved in the 35.25g propylene glycol monomethyl ether, behind nitrogen replacement, make it 125 ℃ of reactions 24 hours, obtain oligomer compounds solution.The oligomer compounds that obtains is carried out gpc analysis, and the result is 2000 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, in the oligomer compounds that obtains by this synthesis example, contain triazinetrione compound with substituting group formula (32) with by the oligomer compounds that is connected basic formula (46) connection triazinetrione ring.

Synthesis example 8

After making single arylolycidyl base cyamelide of 2.0g and the single aryl cyamelide of 1.2g be dissolved in the 13.2g cyclohexanone, reactant liquor is heated to 120 ℃, nitrogen circulates in reactant liquor simultaneously.Then, add the 0.08g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 21 hours as catalyzer.The resultant of reaction that obtains is carried out gpc analysis, and the result is 5800 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, the resultant of reaction that is obtained by this synthesis example contains the have structural unit compound of (61).

Synthesis example 9

After making the single phenyl cyamelide of 2.0g monoene propyl group diglycidyl cyamelide and 1.5g be dissolved in the 14.2g cyclohexanone, reactant liquor is heated to 120 ℃, nitrogen circulates in reactant liquor simultaneously.Then, add the 0.08g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 19 hours as catalyzer.The resultant of reaction that obtains is carried out gpc analysis, and the result is 2400 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, the resultant of reaction that is obtained by this synthesis example contains the compound of (62) structural unit that has formula.

Synthesis example 10

After making 2.0g monoene propyl group diglycidyl cyamelide and 1.0g monomethyl cyamelide be dissolved in the 12.4g cyclohexanone, reactant liquor is heated to 120 ℃, nitrogen circulates in reactant liquor simultaneously.Then, add the 0.08g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 19 hours, obtain to contain the solution of resultant of reaction as catalyzer.

Can infer in addition, the resultant of reaction that is obtained by this synthesis example contains the compound of (63) structural unit that has formula.

Synthesis example 11

After making 2.0g monoene propyl group diglycidyl cyamelide and 2.2g monomethyl dicarboxyl butyl isocyanuric acid ester be dissolved in the 17.4g cyclohexanone, reactant liquor is heated to 120 ℃, nitrogen circulates in reactant liquor simultaneously.Then, add the 0.08g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 19 hours as catalyzer.The resultant of reaction that obtains is carried out gpc analysis, and the result is 12200 by the weight-average molecular weight of polystyrene standard calibration.

Can infer in addition, the resultant of reaction that is obtained by this synthesis example contains the compound of (64) structural unit that has formula.

Synthesis example 12

Make 0.50g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC) and after 1.2g mono carboxylic propyl-dimethyl isocyanuric acid ester is dissolved in the 7.0g dimethyl formamide, reactant liquor is heated to 120 ℃, and nitrogen circulates in reactant liquor simultaneously.Then, add the 0.03g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 20 hours, obtain to contain the solution of the resultant of reaction shown in the formula (65) as catalyzer.

Synthesis example 13

Make 1.8g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC) and after 4.0g mono carboxylic methyl dimethoxy base isocyanuric acid ester is dissolved in the 23.8g NMF, reactant liquor is heated to 120 ℃, and nitrogen circulates in reactant liquor simultaneously.Then, add the 0.1g benzyltriethylammoinium chloride, under nitrogen atmosphere, stirred 20 hours, obtain to contain the solution of the resultant of reaction shown in the formula (66) as catalyzer.

Synthesis example 14

10g cresols-novolac resin (rising sun チバ (strain) goods, trade name ECN1299, weight-average molecular weight 3900) added to make its dissolving in the 80g propylene glycol monomethyl ether.After in this solution, adding 9.7g9-anthroic acid and 0.26g benzyltriethylammoinium chloride, at 105 ℃ of reactions 24 hours, the resin compound of acquisition formula (67).The resultant of reaction that obtains is carried out gpc analysis, and the result is 5600 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 15

Make 6.8g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC) and 12.9g3, after 7-dihydroxy-2-naphthoic acid and 0.37g benzyltriethylammoinium chloride are dissolved in the 80g cyclohexanone, make it, obtain oligomer compounds 130 ℃ of reactions 24 hours.The oligomer compounds that obtains is carried out gpc analysis, and the result is 1400 by the weight-average molecular weight of polystyrene standard calibration.Can infer in addition, in the oligomer compounds that obtains by this synthesis example, contain triazinetrione compound with substituting group formula (37) with by the oligomer compounds that is connected basic formula (53) connection triazinetrione ring.

Synthesis example 16

30g trifluoroethyl methacrylate, 12.3g methacrylic acid and 4.6g methacrylic acid-2-hydroxy propyl ester are dissolved in the 201g propylene glycol monomethyl ether, are warming up to 60 ℃.Then, make reactant liquor in 60 ℃ of insulations, adding 3.3g 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile) was 60 ℃ of reactions 24 hours.Reactant liquor is added drop-wise in water and the ethanol mixed solvent, filters the precipitation of being separated out, obtain the copolymerization macromolecular compound of trifluoroethyl methacrylate and methacrylic acid and methacrylic acid 2-hydroxy propyl ester.The macromolecular compound that obtains is carried out gpc analysis, and the result is 15000 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 17

30g methacrylic acid trichloro ethyl ester, 4.5g methacrylic acid-2-hydroxy propyl ester are dissolved in the 145g propylene glycol monomethyl ether, are warming up to 60 ℃.Then, make reactant liquor in 60 ℃ of insulations, adding 1.7g 2,2 '--azo two (4-methoxyl-2,4-methyl pentane nitrile), 60 ℃ of reactions 24 hours.Reactant liquor is added drop-wise in water and the ethanol mixed solvent, filters the precipitation of being separated out, obtain the copolymerization macromolecular compound of methacrylic acid trichloro ethyl ester and methacrylic acid-2-hydroxy propyl ester.The macromolecular compound that obtains is carried out gpc analysis, and the result is 11000 by the weight-average molecular weight of polystyrene standard calibration.

Synthesis example 18

21g glycidyl methacrylate and 39g methacrylic acid-2-hydroxy propyl ester is dissolved in the 242g propylene glycol monomethyl ether, is warming up to 70 ℃.Then, make reactant liquor in 70 ℃ of insulations, adding the 0.6g azobis isobutyronitrile,, obtaining the solution of the copolymerization macromolecular compound of glycidyl methacrylate and methacrylic acid-2-hydroxy propyl ester 70 ℃ of reactions 24 hours.The copolymerization macromolecular compound that obtains is carried out gpc analysis, and the result is 50000 by the weight-average molecular weight of polystyrene standard calibration.Have in the solution of this macromolecular compound of 20g to 100g, add 10g9-anthroic acid, 0.3g benzyltriethylammoinium chloride and 41g propylene glycol monomethyl ether, at 130 ℃ of reactions 24 hours, the solution of the macromolecular compound of acquisition formula (68).

Embodiment 1

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 1, mix 0.3g HMMM (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 303) and 0.03g p-toluenesulfonic acid pyridine, it is dissolved in 20g propylene glycol monomethyl ether and the 28g methyl lactate forms solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 2

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 2, mix 0.3g HMMM (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 303) and 0.03g p-toluenesulfonic acid pyridine, it is dissolved in 20g propylene glycol monomethyl ether and the 28g methyl lactate forms solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 3

Have 2g to 10g and mix 0.3g HMMM (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 303) and 0.03g p-toluenesulfonic acid pyridine in by the solution of above-mentioned synthetic 3 oligomer compounds that obtain, it is dissolved in 20g propylene glycol monomethyl ether and the 28g ethyl lactate forms solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 4

In 10g has the solution of the macromolecular compound that 2g obtains by above-mentioned synthesis example 4, mix 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name パウダ one リ Application Network 1174) and 0.05g p-toluenesulfonic acid pyridine, it is dissolved in 23g propylene glycol monomethyl ether and the 31g methyl lactate forms solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 5

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 6, mix 0.5g tetramethoxymethylglycoluril and 0.05g p-toluenesulfonic acid pyridine, add the 56.7g propylene glycol monomethyl ether, make its dissolving, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 6

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 7, mix 0.5g tetramethoxymethylglycoluril and 0.05g p-toluenesulfonic acid pyridine, add the 56.7g propylene glycol monomethyl ether, make its dissolving, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 7

In having the solution of the resultant of reaction that 1.2g obtains by above-mentioned synthesis example 8,6g mixes 0.3g HMMM and 0.03g p-toluenesulfonic acid, after adding the 23.7g ethyl lactate, the use aperture is that the tygon system millipore filter of 0.10 μ m filters, using the aperture then is that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution that forms antireflection film.

Embodiment 8～embodiment 12

With above-mentioned same, in having the solution of the resultant of reaction that 1.2g obtains by above-mentioned synthesis example 9～synthesis example 13,6g mixes 0.3g HMMM and 0.03g p-toluenesulfonic acid respectively, after adding the 23.7g ethyl lactate, the use aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 13

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.05g p-toluenesulfonic acid pyridine, 20g propylene glycol monomethyl ether, 59g ethyl lactate and 12g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 14

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.4g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.1g HMMM (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 303), 0.05g p-toluenesulfonic acid pyridine, 16g propylene glycol monomethyl ether, 49g ethyl lactate and 8g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 15

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.3g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.2g HMMM (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 303), 0.05g p-toluenesulfonic acid pyridine, 16g propylene glycol monomethyl ether, 49g ethyl lactate and 8g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 16

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 2.0g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.2g p-toluenesulfonic acid pyridine, 14g propylene glycol monomethyl ether, 43g ethyl lactate and 6g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 17

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.05g 5-sulfosalicylic acid, 12g propylene glycol monomethyl ether, 37g ethyl lactate and 4g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 18

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.09g dinonylnaphthalene sulfonic acid ester, 12g propylene glycol monomethyl ether, 37g ethyl lactate and 4g cyclohexanone, form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 19

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.05g p-toluenesulfonic acid pyridine, 0.09g, form solution by macromolecular compound, 10g propylene glycol monomethyl ether, 30g ethyl lactate and 2g cyclohexanone that above-mentioned synthesis example 16 obtains.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 20

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name サイメ Le 1170), 0.05g p-toluenesulfonic acid pyridine, 0.18g, form solution by macromolecular compound, 10g propylene glycol monomethyl ether, 30g ethyl lactate and 2g cyclohexanone that above-mentioned synthesis example 17 obtains.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Embodiment 21

In 10g has the solution of the oligomer compounds that 2g obtains by above-mentioned synthesis example 15, add 0.8g three-(2, the 3-glycidyl)-isocyanuric acid ester (daily output chemical industry (strain) system, trade name TEPIC), 39g propylene glycol monomethyl ether, 47g propylene glycol methyl ether acetate and form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Comparative example 1

In having the solution of the macromolecular compound that 2g obtains by above-mentioned synthesis example 5,10g mixes 0.5g tetramethoxymethylglycoluril (Mitsui サイテ Star Network (strain) system, trade name パウダ one リ Application Network 1174) and 0.03g p-toluenesulfonic acid, it is dissolved in 37.3g propylene glycol monomethyl ether and the 19.4g cyclohexanone, forms solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Comparative example 2

In having the solution of the resin that 2g obtains by above-mentioned synthesis example 14,10g mixes 0.53g HMMM and 0.05g p-toluenesulfonic acid pyridine monohydrate, make it be dissolved in 14.3g ethyl lactate, 1.13g propylene glycol monomethyl ether and 2.61g cyclohexanone, after forming 9% solution, the use aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Comparative example 3

In 10g has the solution of the macromolecular compound that 2g obtains by above-mentioned synthesis example 18, add 0.3g HMMM, 0.01g p-toluenesulfonic acid, 37.3g propylene glycol monomethyl ether and 19.4g propylene glycol methyl ether acetate, make it form solution.Then, using the aperture is that the tygon system millipore filter of 0.10 μ m filters, and then to use the aperture be that the tygon system millipore filter of 0.05 μ m filters, and modulates the composition solution of formation antireflection film.

Dissolution test in the photoresist solvent

To be applied on the silicon wafer by spin coating by the composition solution that forms antireflection film of embodiment 1～21 and comparative example 1～3 modulation.On electric hot plate, burnt till 1 minute at 205 ℃, form antireflection film (thickness 0.10 μ m).This antireflection film is impregnated into the solvent that photoresist uses, for example in ethyl lactate and the propylene glycol monomethyl ether, confirms to be insoluble in this solvent.

The test that mixes with photoresist

To be applied on the silicon chip by spin coating by the composition solution that forms antireflection film of embodiment 1～6,13～21 and comparative example 1,3 modulation.On hot plate, burnt till 1 minute 205 ℃ of heating, form antireflection film (thickness 0.10 μ m).On the upper strata of this antireflection film for lithography, (シプレ one society's system, trade name UV113 etc.) are coated with by spin coating with commercially available photoresist agent solution.On electric hot plate, heated 1 minute at 120 ℃, after photoresist is exposed, carry out exposure back heating (PEB:PostExposureBake) in 1.5 minutes at 115 ℃.After making development of photoresist, measure the thickness of antireflection film, confirming not have mixing of generation and photoresist layer from the antireflection film for lithography that the composition solution that forms antireflection film by embodiment 1～6,13～21 and comparative example 1,3 modulation obtains.

Equally, on the upper strata that utilizes the formed antireflection film of being modulated by embodiment 7～9 and comparative example 2 of the composition solution that forms antireflection film (thickness 0.23 μ m), (Sumitomo Chemical (strain) society system, trade name PAR710) is coated with by spin coating with commercially available photoresist agent solution.On electric hot plate, heated 1 minute at 90 ℃, after photoresist is exposed, carry out exposure back heating (PEB:PostExposureBake) in 1.5 minutes at 90 ℃.After making development of photoresist, measure the thickness of antireflection film, confirming not have mixing of generation and photoresist layer from the antireflection film for lithography that the composition solution that forms antireflection film by embodiment 7～9 and comparative example 2 modulation obtains.

The test of optical parametric

To coat on the silicon wafer by spin coating by the composition solution that forms antireflection film of embodiment 1～4,13～21 and comparative example 1,3 modulation.On electric hot plate, burnt till 1 minute at 205 ℃, form antireflection film (thickness 0.06 μ m).Then, use the beam split ellipsometer to measure the refractive index under wavelength 248nm (n value) and the attenuation coefficient (k value) of these antireflection films.Show the result in table 2 and table 5.

To coat on the silicon chip by spin coating by the composition solution that forms antireflection film of embodiment 5,6 modulation.On hot plate, burnt till 1 minute at 205 ℃, form antireflection film (thickness 0.06 μ m).Then, use beam split ellipsometer (J.A.Woolam society system, VUV-VASE VU-302) to measure the refractive index under wavelength 157nm (n value) and the attenuation coefficient (k value) of these antireflection films.Evaluation result is shown in table 3.

To coat on the silicon chip by spin coating by the composition solution that forms antireflection film of embodiment 7～12 and comparative example 2 modulation.On hot plate, burnt till 1 minute 205 ℃ of heating, form antireflection film (thickness 0.09 μ m).Then, use the beam split ellipsometer to measure the refractive index under wavelength 193nm (n value) and the attenuation coefficient (k value) of these antireflection films.Show the result in table 4.

The mensuration of dry etching rate

To coat on the silicon wafer by spin coating by the composition solution that forms antireflection film of embodiment 1～21 and comparative example 1～3 modulation.On electric hot plate, burnt till 1 minute at 205 ℃, form antireflection film.Using Japanese サイエ Application テイ Off イ Star Network system RIE then is ES401, using under the condition of CF as dry etching gas, measures dry etching rate.

In addition, equally photoresist agent solution (シプレ one society's system, trade name UV113 and Sumitomo Chemical (strain) system, trade name PAR710) is filmed by being spin-coated on to make on the silicon wafer.Using Japanese サイエ Application テイ Off イ Star Network system RIE then is ES401, using under the condition of CF as dry etching gas, measures dry etching rate.Carry out the antireflection film of embodiment 1～4,13～21 and comparative example 1,3 and the comparison that シプレ one society makes the dry etching rate of photoresist, trade name UV113.The results are shown in table 2 and table 5.Antireflection film and the Sumitomo Chemical (strain) that carries out embodiment 5～12 and comparative example 2 made, the comparison of the dry etching rate of trade name PAR710.The results are shown in table 3 and table 4.

The simulation test of first minimum thickness

Refractive index n value and the attenuation coefficient k value of antireflection film for lithography under wavelength 248nm that use obtains from the composition solution that forms antireflection film by embodiment 1～4,13～21 and comparative example 1,3 modulation, carry out simulation test, calculate first minimum thickness and the reflectivity when using with first minimum thickness.In addition, simulation test is used FINLE Technologies Inc system PROLITH/2.Show the result in table 2 and table 5.

Table 2

Table 3

Table 4

Table 5

Can judge thus, the antireflection film that is obtained by the composition that forms antireflection film of the present invention is that the light of 248nm (embodiment 1～4, embodiment 13～21), 157nm (embodiment 5,6) and 193nm (embodiment 7～12) has fully effective refractive index and attenuation coefficient to wavelength.

Can judge in addition, the selection that photoresist is had very big dry etching rate is than (embodiment 1～21), in addition, compare with existing antireflection film, its anti-reflection effect height more can use (embodiment 1～4 and comparative example 1 and embodiment 13～21 and comparative example 3) with film.Therefore, can shorten the dry ecthing that utilizes of antireflection film and remove the needed time, therefore, can suppress the bad phenomenon of minimizing of thickness that what is called is followed the photoresist layer of removing that utilizes dry ecthing of antireflection film.

As described above, can provide a kind of composition that forms antireflection film by the present invention, its light that is used to form the wavelength that uses in the manufacturing of semiconductor devices shows good light absorption, has very high antireflection light effect, compare with the photoresist layer and to have very big etching speed, do not produce with the photoresist layer and to mix, the die bed organic anti-reflective film of the excellence of the diffusate in resist not during heat drying.

Claims

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.