TWI282908B - Pattern forming method and material for forming underlayer film - Google Patents

Abstract

The solution of this invention is to provide a pattern forming method which is carried out by forming a photoresist underlayer film containing a co-condensed product of a naphthol derivative and dicyclopentadiene as an antireflection film on the substrate to be processed, applying a photoresist composition layer on the underlayer film, irradiating the resist in a pattern circuit region with radiation, developing with a developer solution to form a resist pattern, and processing the underlayer film and the substrate by a dry etching device using the photoresist layer as a mask. The material for forming the underlayer film has the n value of 1.5 to 1.9 and the k value of 0.15 to 0.3 in the refractive index and the absorbance to develop a sufficient antireflection effect in over 200 nm film thickness. The material has an almost equal etching rate for CF4/CHF3 gas and Cl2/BCl3 gas used for processing the substrate to that of a novolac resin and has high etching durability. The resist profile after patterning is also preferable.

Description

1282908 Λι (1) . 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 , , , , , 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体The exposure of ArF excitation (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), etc. is appropriate, and the photoresist pattern formation method. [Inventional Technology] In recent years, with the high integration of LSI and high-speed carbonization, the miniaturization of pattern rules has been demanded. Among them, the currently used lithography using light exposure is widely approaching The wavelength of the source is essentially the boundary of the resolution. In the light source for lithography used in the formation of the photoresist pattern, light exposure using a g-line (43 6 nm) or an i-line (3 65 nm) of a mercury lamp is widely used, and further miniaturization is used. In terms of means, the method of making the exposure light shorter wavelength is considered to be effective. Therefore, for example, in the mass production process of the 6 4Mb DRAM processing method, it is used as an exposure light source instead of a short-wavelength KrF-excited laser (248 nm) of i line (3 65 nm). However, in the manufacture of DRAMs having a fine processing technique (for example, a processing size of 0.1 3 or less) which is necessary for a cumulative degree of 1 G or more, a light source of a shorter wavelength is necessary, in particular, lithography using an ArF-excited laser (193 nm). The surgery is being reviewed. On the one hand, it is known to form a high aspect ratio pattern on a high and low difference substrate, -4- 1282908 (2) 2-layer photoresist method is excellent self-evident, especially, in order to make the two-layer photoresist film with a general alkali When a liquid is imaged, a polymer polyoxyl compound having a hydrophilic group such as a hydroxyl group or a carboxyl group is suitable. In the case of a polyfluorene-based chemically amplified positive photoresist material, a part of the phenolic hydroxyl group of the polyhydroxybenzyl sesquioxane which is a stable alkali-soluble polyoxynoxy polymer is protected by a t-Boc group. It is proposed to use a KrF-excited polyfluorene-based chemically-enhanced positive-type photoresist material in combination with an acid generator for use as a base resin (Japanese Patent Laid-Open No. Hei 7-118651, SPIE vol. 1 925 (1 993) P 3 7 7 etc.). Further, in the case of Ar F excitation laser, it is proposed to use a cyclohexyl carboxylic acid in the form of an acid-unstable group substituted sesquioxane as a positive-type photoresist of the underlayer (Japanese Patent Laid-Open No. 10-324748, the same as 11- Bulletin No. 302382, SPIE vol. 3333-07 1998) P62). Further, in the case of the F 2 laser, a positive-type photoresist having ruthenium sesquioxane in which hexafluoroisopropanol is present in a solvent-based manner is proposed (JP-A-2002-55456). The above polymer contains a polyfluorinated sesquioxane having a trapezoidal skeleton due to polycondensation of a trialkoxysilane or a trihalogenated decane. In the case of the underlayer polymer in which the side chain is laterally grouped, a sand-containing (meth) acrylate-based polymer is proposed (Japanese Patent Laid-Open No. 9-1 093 8 Technology Monthly j. PhotopolymerSci.and, Technol. Vol. 9 No. 3 (1 996) P43 5 -446 ). In the case of a film under the two-layer photoresist method, it is a hydrocarbon compound which is uranium engraved by oxygen gas, and it is necessary to have high etching resistance in order to make the underlying substrate a mask for etching. In the case of oxygen etching, it is necessary to form only a hydrocarbon group containing no germanium atoms. In addition, it is necessary to improve the line width controllability of the upper layer of the yttrium-containing atom. 5 - 1282908 (3), and to reduce the unevenness of the sidewall of the pattern caused by the standing wave and the collapse of the pattern, it is necessary to function as an anti-reflection film. Specifically, the reflectance from the underlayer film to the photoresist film needs to be suppressed to less than 1%, and the underlying anti-reflection film for the single-layer photoresist process, even under polyfluorene or In the case of a highly reflective substrate such as aluminum, the material having an optimum refractive index (η値) and extinction coefficient (k値) can be set to a suitable film thickness, and the reflection from the substrate can be reduced to less than 1%. The effect. For example, at a wavelength of 193 nm, the refractive index of the photoresist film is 1.7, and the refractive index (real part of the refractive index) η of the lower anti-reflection film is 1.5, and the extinction coefficient (imaginary part of the refractive index) k is When the film thickness is 42 nm, the reflectance is 0.5% or less (refer to Fig. 1). However, in the case where the bottom layer has a difference in height, the film thickness of the antireflection film greatly changes in height difference. The anti-reflection effect of the bottom layer is not only the absorption of light, but also the dry effect caused by setting the optimum film thickness. Therefore, the anti-reflection effect of the first bottom edge of 40~45 nm with strong cognac effect is so high, but The reflectance changes due to variations in film thickness. A material for improving the molecular weight of the base resin of the antireflection film material to suppress the film thickness variation in the height difference to improve conformality is proposed (JP-A-10-9072), and the molecular weight of the base resin. When it is high, there is a problem that the pinhole is likely to occur after the spin coating, or there is a problem that the filtration cannot be performed, and the viscosity changes over time to change the film thickness, or the crystal precipitates at the tip of the nozzle. problem. Moreover, those who can exhibit shape retention are limited to low height differences. -6 - (4) 1282908 Next, the film thickness (i70nm or more) of the third base or less which is relatively small due to the variation in film thickness is used, and the film is between k値0·2 and 0.3. When the thickness is I70 nm or more, the reflectance variation with respect to the change in film thickness is small, and the number of reflectances of 1.5% or less can be suppressed. However, when the etching load of the upper photoresist film is considered, the thick film of the antireflection film has its boundary, and the thick film of the second base having a charge of about 100 nm or less is also a boundary. Further, the underlayer of the antireflection film is a transparent film such as an oxide film or a nitride film, and further has a height difference under the transparent film. Even if the surface of the transparent film is planarized by CMP or the like, the transparent film is The film thickness changes. In this case, the film thickness of the antireflection film thereon is constant, and when the film thickness of the underlying transparent film of the antireflection film is changed, the film thickness of the minimum reflectance is only the film thickness portion of the transparent film. Even when the film thickness of the antireflection film is set to the lowest reflection film thickness when the underlayer is a reflection film, the reflectance becomes high due to the variation in the film thickness of the transparent film. The material of the antireflection film can be roughly classified into an inorganic system and an organic system. The inorganic system is exemplified by a SiON film. This is formed by CVD or the like caused by a mixed gas of decane and ammonia, and has a large etching selectivity with respect to the photoresist film. Therefore, there is an advantage that the etching of the photoresist is small, but it is difficult to peel off. There are restrictions on the application. Further, since the positive-type resist is liable to cause a footing due to the inert substrate containing a nitrogen atom, the negative-type photoresist has a drawback that an undercut profile is liable to occur. The organic system is not necessary for the special device such as CVD or splatter which can be spin-coated, and the edge of the photoresist film can be peeled off at the same time. Since the 1282908 (5) does not cause the hemming bottom (hemming bottom) The shape is flat, so that the adhesion to the photoresist film is good, and an antireflection film having a plurality of organic materials as a base is proposed. For example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in Japanese Patent Publication No. 7-6961-1, an alkali-soluble resin and a light-absorbing agent, or a product described in the specification of US Pat. No. 529,468 A reaction product containing a resin binder and a methylol melamine-based thermal crosslinking agent described in JP-A-6-181643, the reaction product of the butadiene anhydride copolymer and the diamine type light-absorbing agent. An acryl resin base type having a carboxylic acid group, an epoxy group, and a light absorbing group in the same molecule, which is described in JP-A-6-1 1 8 65, and a methylol group described in JP-A-8-8 1 1 5 A melamine and a diphenyl ketone-based light absorbing agent are used, and a low molecular weight light absorbing agent or the like is added to a polyvinyl alcohol resin as described in JP-A-8-79595. These are all employed by adding a light absorbing agent to the binder polymer or introducing the substituent into the polymer. However, since a plurality of light absorbing agents have an aromatic group or a double bond, the dry etching resistance is increased by the addition of the light absorbing agent, and the dry uranium engraving ratio of the photoresist cannot be improved. In the case of miniaturization, the thin film formation of the photoresist can be promoted. Further, in the next-generation ArF exposure, the uranium resistance of the photoresist is lowered due to the use of the propylene or alicyclic polymer in the photoresist material. Further, as described above, there is a problem that the film thickness of the antireflection film must be made thicker. Therefore, etching is an extremely important problem, and an antireflection film having a high etching selectivity with respect to the photoresist etching speed, that is, an etching speed is desired. On the one hand, in the underlying film for the 2-layer photoresist process, the function required for the anti-reflection film is not the same as that of the single-layer photoresist. For 2-layer photoresist process -8- 1282908 (6) The underlayer film is used as a mask when etching the substrate, and must have high uranium resistance under the condition of substrate etching. In the single-layer photoresist process, the anti-reflection film is required to have a fast etching speed in order to reduce the load of the single-layer photoresist, and the opposite characteristic is also required. Further, in order to ensure sufficient substrate etching resistance, the film thickness of the underlayer film must be equal to or thicker than the thickness of the single layer photoresist to 300 nm or more. At a film thickness of 300 nm or more, the change in reflectance due to a change in film thickness is substantially concentrated, and the antireflection effect due to phase difference control cannot be expected. Here, the calculation results of the reflectance up to a film thickness of 500 nm are shown in Figs. 2 and 3. Assuming an exposure wavelength of 193 nm, the resistive upper film has n 値 of 1.74 and k 値 of 0.02. In Fig. 2, k値 of the underlayer film is fixed at 0.3, the x-axis is η値, the horizontal axis is the film thickness, and η値 is in the range of 1.〇~2.0, and the film thickness is varied in the range of 〇~50Onm. The substrate reflectance is expressed. In the case of assuming a lower film of two layers of photoresist having a film thickness of 30 Onm or more, a range of a refractive index of 1.6 to 1.9 which is the same as or slightly higher than that of the upper photoresist film, the optimum reflectance of 1% or less is presence. In Fig. 3, the reflectance when η値 is fixed at 1.9, and k値 is varied in the range of 0.1 to 0.8. The k 値 is in the range of 0.24 to 0.15 so that the reflectance becomes 1% or less. On the one hand, the optimum k 防 of the antireflection film for a single-layer photoresist used for a film of 40 nm is 0.4 to 0.5, which is different from the optimum k 2 of the lower layer of the two layers of photoresist above 300 nm. In the lower layer of the two-layer photoresist, it can represent a lower k値, that is, a higher transparent underlayer film is necessary. Here, as a film forming material for 193 nm, a copolymer of polyhydroxystyrene and propylene 1282908 (7) as disclosed in SPIE Vol. 4345 P50 (2001) is reviewed, and polyhydroxystyrene has a very high at 193 nm. Strong absorption, the substance alone k 値 is 0.6 前后 high. Therefore, since k 値 is almost copolymerized with propylene, k 値 is adjusted to 0.25 before and after. However, compared with polyhydroxystyrene, the etching resistance in the uranium engraving of propylene is weak, and a certain ratio of propylene must be copolymerized due to a decrease in k?, with the result that the etching resistance of the substrate during uranium engraving is considerably lowered. Feed resistance, not just the etching speed, but also the surface roughness after etching. The copolymerization of propylene makes the surface roughness after engraving larger and more important. Compared with the benzene ring, the naphthalene ring is one of those having high transparency and high etching resistance at 93 nm. In JP-A-2002-1-4474, a film having a naphthalene ring and a photoresist ring of an anthracene ring has been proposed. However, the naphthol copolymerized phenolic enamel resin and the polyethylene naphthalene resin have a k 値 of 0.3 to 0.4, and transparency of 0.1 to 0.3 of the target is not achieved, and transparency must be further improved. Further, the naphthol copolymer phenolic enamel resin and the polyethylene naphthalene resin have a low η 193 at 193 nm, and the results of the measurement by the present inventors, the naphthol copolymer phenolic enamel resin can be up to 1.4, in the polyethylene naphthalene resin. Can be up to 1.2. In the phthalocyanine polymer shown in JP-A No. 200, No. 4,293, and the phthalocyanine polymer shown in the publication No. 2002-2 1 4777, η 値 is low and z 値 is high at 19 3 nm as compared with the wavelength of 248 nm, and the target enthalpy cannot be achieved. A film of η 値 high, k 値 low transparency, and high etching resistance is desirable. Here, Japanese Patent Publication No. Hei 6-202317, the same as No. 8-1795-02, the same as No. 8-220750, the same as No. 8-292565, and No. 9-15855, the copolymer of cresol and dicyclopentadiene is The i-line resist of the bottom layer, in the case of higher transparent phenolic enamel resin, copolymerization with p-cyclopentadiene is being reviewed. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. On the other hand, in Japanese Patent Publication No. Hei 6-80760, the same as the publication No. 7-5302, a photoresist composition in which an an aldehyde is condensed with an aldehyde is proposed. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. Japanese Patent Publication No. Hei 9- 1 1 093 No. 8-A. [Patent Document 7] Japanese Patent Publication No. 5294680 (Patent Document 8) Japanese Patent No. 5294680 (Patent Document 9) Japanese Patent Publication No. 6_1 1 863 1 [Patent Document 10] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document No. 1] [Patent Document No. 8 - 2,075,075] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 6-80760 (Patent Document No. 2). -5 3 02 [Non-Patent Document 1] SPIE vol. 1925 (1 993) p377 [Non-Patent Document 2] SPIE vol. 3333 ( 1998) p62 [Non-Patent Document 3] Photopolymer Science and Technology Monthly J. PhotopolymerSci. and Technol. V〇1.9N0.3 (1 9 9 6 ) p 4 3 5 [Non-Patent Document 4] SP IE V 01.434 5 p5 0 (200 1 ) [Disclosed from the Invention] [Problems to be Solved by the Invention] The present invention has been made to solve the problems, and in particular, as an underlayer film for a ruthenium-containing two-layer photoresist process, it is possible to provide an excellent antireflection film and polyhydroxybenzene. Ethylene, cresol novolac lacquer, naphthol phenolic enamel paint, etc., which have high transparency, optimum η値, k値, and excellent film formation resistance in substrate processing, and pattern formation method. [Means for Solving the Problem] The inventors of the present invention found that the copolymer of a naphthol derivative and a pentylene pentadiene has an optimum η 値, k 値 and etch at 93 nm in order to achieve the above objective. It is also excellent in patience, and it is a desirable material as a lower film for a ruthenium-containing two-layer photoresist process, and thus the present invention has been completed. That is, in the present invention, as a novel underlayer film applicable to a layer-by-layer process, especially at a wavelength of 193 nm, a film thickness of 200 nm is excellent in antireflection effect on -12-(10) 1282908, and etching is performed. Excellent resistance, the co-condensation of a naphthol derivative and a cyclopentadiene co-condensation phenolic enamel resin as a material of the underlayer, which has an optimum η値, k値, and can suppress a film thickness of 2 〇〇 nm. The above-mentioned substrate reflection is excellent in etching resistance under the conditions of substrate etching. Therefore, the present invention provides the following pattern forming method and the use of the underlayer film forming material. 1 . A pattern forming method, characterized in that, as an antireflection film, a photoresist underlayer film containing a cocondensate of a naphthol derivative and a cyclopentadiene is applied to a substrate to be processed, and the underlayer film is used. The layer of the photoresist composition is applied, the radiation is irradiated in the field of the pattern circuit, the photoresist pattern is formed by the development of the developing liquid, and the photoresist layer is used as a mask by the dry etching device to perform the underlayer film and the substrate to be processed. The processor. 2. The method for forming a pattern according to claim 1, wherein the photoresist composition contains a polymer containing a ruthenium atom, and the photoresist layer is used as a mask for dry etching of the underlayer film, and oxygen gas is used. The etching gas of the main body is performed. 3. The pattern forming method according to the second aspect of the patent application, wherein after the oxygen gas is etched, the underlayer film is formed into a mask, and the substrate is subjected to dry etching. 4 . An underlayer film forming material characterized by, for example, a photoresist underlayer film forming material used in the pattern forming method of claim 1, 2 or 3, wherein the naphthol derivative and the cyclopentadiene The cocondensate is represented by the following general formula (1) or (2), -13- (11) 1282908

Γ R8 R1

(wherein R1 to R8 are independently a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 6 carbon atoms, and a substitutable alkoxy group having 1 to 6 carbon atoms; 2 to 6 carbon atoms; The substituted alkoxycarboxy group, a substitutable aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group or a glycidyl group, and m and η are positive integers). 5 · If the film forming material is under the fourth paragraph of the patent application, it further contains 'organic solvent, crosslinking agent and acid generator. . [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. In the pattern forming method of the present invention, in the aspect of the antireflection film, a photoresist underlayer film containing a cocondensate of a naphthol derivative and a cyclopentadiene is applied to a substrate, and a photoresist composition is applicable to the underlayer film. The layer of the object is irradiated with radiation in the field of the pattern circuit, and is developed by a developing liquid to form a photoresist pattern. In the dry etching apparatus, the photoresist layer is used as a mask to process the underlying film layer and the substrate, and is used herein. The underlayer film forming material is an essential component of the underlayer polymer of (A) a cocondensate of a naphthol derivative and a cyclopentadiene, preferably containing (B) an organic solvent, -14-1282908 (12 (C) Crosslinking agent, (D) Acid generator. Here, in the copolymer of the naphthol derivative of the component (A) and the cyclopentadiene, it is preferred to be represented by the following general formula (1) or (2).

In the above formula, 'R1 to R8 are mutually independent hydrogen atoms, a hydroxyl group, a substitutable alkyl group having 1 to 6 carbon atoms, a substitutable alkoxy group having 1 to 6 carbon atoms, and a carbon atom number of 2 to 6 may be substituted. Alkoxycarboxyl group, substitutable aryl group having 6 to 10 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, isocyanate group

Or epoxy propyl. m, η is a positive integer. Here, the naphthol derivative of the repeating unit of the general formulae (1) and (2) can be exemplified, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4 -methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxynaphthalene, anthracene, 7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. Methyl-hydroxy-naphthyl-carboxylate. The cyclopentadiene-based and cyclopentadiene 2-mers are present as two isomers of an inward form (endo) and an exo form (exo), but the present invention is used as a raw material for the resin. The diene may be either an isomer or a mixture of two isomers. In the case of using a mixture of isomers, the ratio of the isomers is not particularly limited. -15- (13) 1282908 The repeating unit of the general formulae (1) and (2) is obtained by subjecting a cyclopentadiene to a naphthol to an addition reaction in the presence of an acid catalyst. The acid catalyst used in the reaction may, for example, be an alcoholic compound of boron trifluoride or a mineral acid such as Lewis acid, hydrochloric acid, nitric acid or sulfuric acid such as aluminum chloride, methanesulfonic acid, n-butylsulfonic acid or benzenesulfonic acid. , p-toluenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, mesitylene sulfonic acid, etc., sulfonic acid, trifluoromethane methanesulfonic acid, nonafluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, etc. Perfluorosulfonic acid-like super acid, a perfluoroalkane polymer having a terminal sulfonic acid group such as Nafion, an anion exchange resin such as polystyrene having a sulfonic acid residue, or the like. In particular, methane methanesulfonic acid, tosy sulfonic acid (to sy late), and trifluoromethanesulfonic acid are preferred, and the amount thereof used is 0.01 to 10% by weight, preferably 〇, based on the raw material in the case of methane methanesulfonic acid. The range of 5 to 5 wt% in the case of trifluoromethane methanesulfonic acid is in the range of 〇. 0 0 0 1 to 5 wt%, preferably 0.00 0 5 to 1 wt%. The ratio of naphthol to pentacyclopentadiene is from 0.1 to 2.0 moles, preferably from 0.2 to 1.8 moles, per mole of naphthol. The polymer obtained by co-condensation of a naphthol derivative and a pentylene pentadiene of the present invention is suitable for use as a lower layer film, and further co-condensable with a phenol. The phenols mentioned herein may, for example, be phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol or 3,4-xylenol. 3,5-xylenol, 2,4-xylenol, 2,6-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2·tert-butylphenol, 3-tertiary butyl phenol, 4-tributyl phenol, resorcinol, 2-methyl resorcinol, 4-methyl resorcinol, 5 · methyl resorcinol, catechu Phenol, 4-tributyl catechol, -16- (14) 1282908 2-methoxyphenol, 3-methoxyphenol, 2-propyl phenol, 3-propyl phenol, 4-propyl phenol , 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tributyl-5-methyl-phenol, coke bake (pyrogallol), thyme S (thymol), iso thymol and the like. Other examples of the monomer copolymerizable with naphthol include dihydroanthracene, hydroxynaphthalene, acenaPhthylene, and biphenyl. It is also possible to add a copolymer of three or more of these. Further, the ratio of the above-mentioned co-condensed phenol unit is preferably 60 mol% or less, particularly preferably 〇 50 50 mol%, of the underlying polymer containing the cocondensate of the naphthol derivative and the p-cyclopentadiene. The reaction can be classified into an addition reaction of a cyclopentadiene with a hydroxyl group of naphthol, a first stage of etherification, and a second stage of formation of a naphthol resin by a transfer reaction. The reaction temperature is in the range of 20 to 200 ° C, preferably 4 〇 to 16 (the range of TC. After the reaction is completed, the unreacted naphthol compound can be distilled off by any method to obtain naphthol-cyclopentylene. When the diene resin is used for the purpose of the present invention, it is desirable to introduce a washing process. The washing method may be any method, for example, using a metal hydroxide to be insoluble in an alkali metal salt method. As a method of removing the components of water, an aromatic hydrocarbon such as toluene or xylene, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, a pentanol, an isopentyl alcohol or a heptanol can be used. a method in which an organic solvent such as heptyl alcohol, octanol or isooctyl alcohol is washed with water, and the above organic solvent is used to wash the diluted hydrochloric acid, and 1 2 2 -dichloroethane or chloroform is used. A solvent such as methyl cellosolve, ethyl cellosolve, dimethylformamide or dimethylacetamide is treated with a sorbent -17-(15) 1282908 agent such as tannin extract, alumina or activated carbon. Method, etc. by any one of the methods, or a combination of the methods, etc. Or an acidic component, an impurity such as a metal ion, and the like are preferably minimized. The weight average molecular weight is preferably in the range of 1,500 to 200,000, preferably in the range of 2,000 to 10,000. The molecular weight distribution is not particularly limited, and is divided by It is possible to remove low molecular weight and high molecular weight to reduce the degree of dispersion, and to mix two or more kinds of phenol-penecyclopentadiene resins having different molecular weights and dispersities, or two or more kinds of phenol-polycyclic rings having different composition ratios. It is also possible to mix the pentadiene resin. In order to further improve the transparency of the naphthol-cyclopentadiene copolymer resin of the present invention, hydrogenation can be carried out. The preferred hydrogenation ratio is an aromatic group such as naphthol. 50 mol% or less. The base resin for a film forming material of the present invention is characterized by containing a naphthol-p-cyclopentadiene resin, but may be exemplified by the above-mentioned antireflective film material blended with a conventional polymer. The naphthoquinone-p-cyclopentane resin has a glass transition temperature of 150 ° C or more, and this material alone may have poor buried characteristics of deep holes such as Wa holes. The side that creates the void A method of embedding a polymer having a low glass transition temperature, performing a hot air blowing at a temperature lower than the crosslinking temperature, and embedding the resin in the bottom of the hole (Japanese Laid-Open Patent Publication No. 2000-294504). a low-transfer temperature of the mouth material, especially a glass transition temperature of below 180 ° C, especially a polymer of 1 q 〇~1 7 〇C, such as propylene derivatives, vinyl alcohol, vinyl ethers, allyl groups Ethers, styrene derivatives, allylbenzene derivatives, olefins such as ethylene, propylene, butylene, etc., polymers obtained by metathesis ring-opening polymerization, etc., can be blended with -18-(16) 1282908 to make glass The transfer temperature is lowered, and the embedding property of the blind via is improved. In this case, the blend ratio of the naphthol derivative to the cyclopentadiene co-condensate to the polymer of the above low glass transition temperature is in the weight ratio of 1 : 0.1 to 1:10, especially 1:0.2 to 1:5 is preferred. In another method for lowering the glass transition temperature, a hydroxyl group having a hydroxyl group of a naphthol pentadiene phenol oxime resin may be exemplified by a linear chain having a carbon number of 1 to 20, a branched or cyclic alkyl group. A method in which an acid unstable group such as a tertiary butyl group, a tertiary pentyl group or an acetal is substituted with an ethyl hydrazino group or a trimethyl ethane group. The substitution ratio at this time is in the range of 10 to 60 mol%, preferably 15 to 50 mol%, based on the hydroxyl group of the naphthol pentene pentadiene phenol oxime resin. One of the properties required for the underlying film containing the antireflection film can be exemplified by no mixing with the photoresist, and no diffusion of the low molecular component of the photoresist layer [Pro c. SPIE Vol. 2195, P225-229 (1994)]. In order to prevent this from occurring, a method of thermally crosslinking by baking after spin coating of an antireflection film is generally employed. Therefore, in the case where a crosslinking agent is added to the components of the antireflection film material, a method of introducing a crosslinkable substituent into the polymer is employed. Specific examples of the crosslinking agent which can be used in the present invention are as follows, which are selected from the group consisting of a melamine compound substituted with at least one group of a methylol group, an alkoxymethyl group, a decyloxymethyl group, a guanine compound, an acetylene urea compound or a urea. a compound containing a double bond such as a compound, an epoxy compound, an isocyanate compound, an azide compound or an alkene group, etc., which may be used as an additive, but may be introduced as a pendant in a polymer side chain. Further, the hydroxyl group-containing compound -19- 1282908 (17) can also be used as a crosslinking agent. Among the above compounds, the epoxy compound can be exemplified as follows, tris(2,3-epoxypropyl)isocyanate, trimethylolethanetriepoxypropyl ether, trimethylolpropane triepoxy Propyl ether, trishydroxyethylethane triepoxypropyl ether, and the like. The melamine compound is specifically exemplified by a compound of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, hexamethylene hydroxymethyl group, methoxymethylated compound, and a mixture thereof, hexamethoxyethyl 1 to 6 methoxymethylated compounds of melamine, hexamethoxymethyl melamine, hexamethylol melamine, or a mixture thereof, or the like. In the case of a guanamine compound, one to four hydroxymethyl groups of tetramethylol guanamine, tetramethoxymethylguanine, and tetramethylol guanamine can be exemplified by methoxymethyl. The compound of the group and the mixture thereof, tetramethylol guanamine, tetradecyl guanine, and hydroxymethyl group of tetramethylol guanamine are methylated by oxime Compounds, mixtures thereof, and the like. As the acetylene urea compound, one to four methoxymethyl groups of tetramethylol acetylene urea, tetramethoxy acetylene urea, tetramethoxymethyl acetylene urea, tetramethylol acetylene urea, and hydroxymethyl group can be exemplified. A compound of the group, or a mixture thereof, 1 to 4 of a methylol group of tetramethylol acetylene urea, or a mixture thereof, or a mixture thereof. The urea compound may, for example, be a compound in which methoxymethyl group of 1,4-methylurea, tetramethoxymethylurea, and 1,4-methylurea is methoxymethylated or Mixture, tetramethoxyethylurea, and the like. In the case of the compound containing an olefinic ether group, ethylene glycol divinyl ether, triethylene glycol divinyl ether, hydrazine, 2, propylene glycol divinyl ether, hydrazine, 4·butylene glycol divinyl ether, tetra-butylene can be exemplified. Glycol divinyl ether, neopentyl glycol divinyl ether, tri-20-(18) 1282908 methylolpropane trivinyl ether, hexanediol divinyl ether, hydrazine, 4-cyclohexanediol divinyl ether, new Pentaerythritol trivinyl ether, neopentyl alcohol tetravinyl alcohol, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like. In the case where the hydroxyl group of the naphthol-penecyclopentadiene resin of the general formula (1) or (2) is substituted by a glycidyl group, the addition of a hydroxyl group-containing compound is effective. In particular, a compound having two or more hydroxyl groups in the molecule is preferred. For example, naphthol phenolic enamel paint, m- and cresol novolac lacquer, naphthol-cyclopentadiene phenolic enamel paint, and p-cresol-cyclopentadiene phenolic enamel paint, 4,8-double ( Hydroxymethyl)tricyclo[5.2.1. 02·6]-nonane, neopentyl alcohol, 1,2,6-hexanetriol, 454,4,-methyleneidene tricyclohexanol ,4,4'-[1-[4-[1-(4-hydroxycyclohexyl)-1-methylethyl]phenyl]ethylidene]bicyclohexanol, [1,1'-dicyclohexyl ]-4,4'-diol, methylene dicyclohexanol, decalin-2,6-diol, [1,1'-dicyclohexyl]-3,3'4,4'-tetrahydroxy Etc. alcohol-containing compound, bisphenol, methylene bisphenol, 2,2'-methylenebis[4-methylphenol], 4,4'-methylene-bis[2,6-dimethyl Phenol], 4,4'-(1·methyl-ethylene)bis[2-methylphenol], 4,4'-cyclohexylene bisphenol, 4,4'-(1,3-dimethyl Butyl butyl), bisphenol, 4,4'-(dimethylethylene) bis[2,6-xylenol], 4,4'-oxybisphenol, 4,4'-methylene bisphenol, Bis(4-hydroxyphenyl)methanone, 4,4,-methylenebis[2-cresol], 4,4'-[1,4-phenylenebis(1-methylethylidene) ]double , 4,4'-(1,2-ethanediyl)bisphenol, 4,4'·(diethylsilylene)bisphenol, 4,4'-[2,2,2- Trifluoro-1-(trifluoromethyl)ethylidene]bisphenol, 4,4',4"-methylenetriphenol, 4,4'-[1-(4-hydroxyphenyl)-1- Methyl ethyl]phenyl]ethylidene]bisphenol, 2,6-bis[(2-hydroxy-5-tolyl)methyl]·4-methylphenol, (19) 1282908

4,4',4"-Subethyltris[2-methylphenol], 4,4',4''-ethylidenetriphenol, 4,6-bis[(4-hydroxyphenyl)methyl] 1,3_Benzenediol, 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol], 4,4',4",4"'·( 1,2-ethyldiylidene)tetraphenol, 4,4f,4'',4'''-ethylenediphenyl)tetrakis[2-methylphenol], 2,2'-methylene double 6·[(2-hydroxy-5-tolyl)methyl]-4-methyl-phenol], 4,4',4",4'"- (1,4-phenylene secondary methyl Metyridine) tetraphenol, 2,4,6-tris(4-hydroxyphenylmethyl)1,3-benzenediol, 2,4',4''-methylenetriphenol, 454',4" -(3-methyl-1-propene__3-ylidene 11 (161^) trisphenol, 2,6-bis[(4-hydroxy-3-chlorophenyl)methyl]-4-fluorophenol, 2,6-bis[4-hydroxy-3-fluorophenyl]methyl]-4-fluorophenol, 3,6-bis(3,5-dimethyl-4-hydroxyphenyl)methyl"1 , 2-Benzenediol, 4,6-double"

(3,5-Dimethyl-4-hydroxyphenyl)methyl"1,3-benzenediol, p-methylcup aryl[4]hydrocarbon, 2,2'-methylenebis[6-[ ( 2,5/3,6-Dimethyl-4/2-hydroxyphenyl)methyl]-4-methylphenol, 2,2'-methylenebis[6-[(3,5-dimethyl) 4-hydroxyphenyl)methyl]-4-methylphenol, 4,4',4",4"'-肆[(1_methylethylidene) bis(1,4-cyclohexylene) (hexylidene))]-phenol, 6,6f-methylenebis[4-(4-hydroxyphenylmethyl)-1,2,3-benzenetriol, 3,3,,5,5,-four A phenolic low nucleus such as [(5-methyl-2-hydroxyphenyl)methyl]-[(1,1'-biphenyl)-4,4'diol]. The amount of the crosslinking agent to be used in the present invention is preferably from 5 to 50 parts, particularly preferably from 10 to 40 parts, per 100 parts by weight (parts by weight) of the base polymer (total resin portion). When there are less than 5 parts, there is a case where it is mixed with the photoresist, and when it exceeds 50 parts, there is a case where the antireflection effect is lowered or the film after the crosslinking is cracked. -22- (20) 1282908 In the present invention, an acid generator which further promotes a crosslinking reaction caused by heat or the like can be added. The acid generator generates acid due to thermal decomposition, and acid is generated by light irradiation, but any one may be added. The acid generator used in the present invention may, for example, be i) the following general formula (Pla-1), (Pla-2), (Pla-3) or (Plb) key salt, Π) the following general formula ( a diazomethane derivative of P2), iii) an ethylenediazine derivative of the following general formula (P3), iv) a double-milled derivative of the following general formula (P4), V) of the following general formula (P5) Sulfonic acid ester of N-hydroxy quinone imine compound, vi ) /3 - keto sulfonic acid derivative, vii) di-milled derivative, viii) nitric acid sulfonate derivative, ix) sulfonate derivative, etc. .

(wherein, Rim, Rioib, and r1g1c each represent a carbon atom; a straight-bonded 'branched chain or cyclic alkyl group, alkenyl group, pendant oxyalkyl group or pendant oxyalkenyl group, carbon atom; An aryl group of 6 to 20 or an aromatic or aryloxyalkyl group having 7 to 12 carbon atoms, and a part or all of one of the hydrogen atoms of the group may be substituted by an alkoxy group or the like. R 1 01 b and R 1 0 1 e may form a ring, and in the case of forming a ring, RlGlb and R1Gle each represent an olefin group having 1 to 6 carbon atoms. K· represents a non-nucleophilic counter ion. RlGld, RlGle, RlGlf, Rl〇lg, -23-(21) 1282908 denotes the addition of a hydrogen atom to Rl〇ia, R1Glb, R1Gle. Rule 1()1(1 and R1()le, Rl(Ud and R1()lf can each In combination with the formation of a ring, in the case of forming a ring, 111()1(1 and R1Gle and &1{)1 (1 and & 1()16 and RlGlf represent an olefin group having 3 to 10 carbon atoms.)

The above Ri〇la, R1Glb, R101c, R1()ld, R1〇le, R1〇lf, Ri〇U may be the same or different from each other, and specifically, in terms of an alkyl group, a methyl group, an ethyl group, Propyl, isopropyl, n-butyl, secondary butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, n-decyl, adamantyl and the like. The alkenyl group may, for example, be a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group. The oxyalkyl group may, for example, be a 2-oxycyclopentyl group, a 2-oxycyclohexyl group or the like, a 2-oxypropyl group, a 2-cyclopentyl-2-oxyethyl group or a 2-cyclohexyl group. 2-Oxoethyl, 2-(4-methylcyclohexyl)-2-oxyethyl, and the like. The aryl group may, for example, be a phenyl group, a naphthyl group or the like, or a p-methoxyphenyl group, a m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a tert-butoxyphenyl group, or a tertiary intermediate. Alkoxyphenyl such as butoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tributylphenyl, 4-butyl An alkane group such as a phenyl group or a xylyl group, a phenyl group, a methyl naphthalene group such as an alkylnaphthyl group such as a methoxyphenyl group, a methoxynaphthyl group or an ethoxynaphthyl group; a dialkoxynaphthyl group such as a naphthylnaphthyl group such as a naphthyl group or a diethylnaphthyl group, a dimethoxynaphthyl group or a diethoxynaphthyl group. The arylalkyl group may, for example, be a styrene group, a phenylethyl group or a phenethyl group. The aryloxyalkyl group may, for example, be 2-phenyl-2-oxoethyl, 2-(p-naphthyl-2-oxoethyl, 2-(2-caiyl)-side oxyethyl, etc. The group 2 - side oxyethyl group, etc. The non-nucleophilic counter ion of κ- -24- (22) 1282908 may, for example, be a halide ion such as a chloride ion or a bromide ion, or a trifluoromethanesulfonic acid. , 1,1,1-trifluoroethane sulfonate, fluoroalkane sulfonate such as nonafluorobutane sulfonate, p-toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, An alkanesulfonate such as an arylsulfonate such as 1,2,3,4,5-pentafluorobenzenesulfonate, a methanesulfonate or a butanesulfonate. (Pla-Ι) and (Pla- 2) It has two effects of photoacid generator and thermal acid generator, but (P1 a-3) acts as a thermal acid generator. R102a !R102b

Rl〇4a_st^Rl〇3_g+_Ri〇4b Κ: κ: (Plb) (wherein R1G2a and R1G2b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R1G3 represents a linear, branched or cyclic olefinic group having 1 to 10 carbon atoms. R1() 4a each represents a carbon atomic number of 3 to 7 - a side oxygen group. K - represents a non-nucleophilic pair Specific examples of the above R1G2a and R1G2b include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, a heptyl group, and the like. Octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. In the case of R103, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, an anthranylene group, a 1,4-cyclohexylene group, and 1, 2-cyclohexylene, anthracene, % cyclopentylene, 1, 4-cyclooctylene, 1,4-cycloheximide monomethylene, and the like. In the case of r1〇", R10 4 b, a 2-oxypropyl group, a 2-oxycyclopentyl group 2 side-oxycyclohexyl group, a 2-oxocycloheptyl group, etc. may be mentioned. · 〗 〖, (pla-2) and (Pla-3) are the same as those described. -25- (23) 1282908 , ίί2 R105—S02~C-S02~R106 (P2) (where R1G5, R1G6 Is a linear, branched or cyclic alkyl or halogenated alkyl group, an aryl or halogenated aryl group having 6 to 20 carbon atoms, or a aryl group having 7 to 12 carbon atoms)

Rl〇5, Rl〇6 alkyl group can be exemplified by methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tert-butyl, pentyl, hexyl, heptyl, octyl Base, pentylene, cyclopentyl, cyclohexyl, cycloheptyl, n-decyl, adamantyl and the like. The halogenated alkyl group may, for example, be a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1·trichloroethyl group or a nonafluorobutyl group. The aryl group may, for example, be phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tertiary butoxyphenyl or m-butoxy Alkoxyphenyl such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, ethylphenyl, 4-tributylphenyl, 4-butylphenyl, dimethylbenzene An alkylphenyl group. The halogenated aryl group may, for example, be a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5 pentafluorophenyl group or the like. The aralkyl group may, for example, be a benzyl group or a phenethyl group.

| I ri〇5_s〇2 一〇一N==c:—c=3Ni 一Ο一S02 一:R107 (P3) (wherein R1G7, R1G8, and R1G9 are linear chains of 1 to 12 carbon atoms, a branched or cyclic alkyl or halogenated alkyl group, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R1()8, R109 may be bonded to each other to form a branched or cyclic alkyl group or a halogenated alkyl group. In the case of a ring-shaped structure, R108 and R1G9 each represent a linear or branched chain olefin group having 1 to 6 carbon atoms in R 1 0 7 , R 1 0 8 , and R 1 0 9 . The alkyl group, the halogenated alkyl group, the aryl group, or the halogenated -26-(24) 1282908 aryl group or the aralkyl group may, for example, be the same as those described for R1G5 and R1G6. Further, in R1()8, R1 The olefin group of (9) may, for example, be a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or the like.

Rl〇la I-R101b

II II Ο ο (Ρ4) (where Rim, R^lb are the same as above.) Ο ιι

R110/N-O-SO2-Rm

C

II O (PS)

(wherein R11G represents a aryl group having 6 to 10 carbon atoms, an olefin group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms; or a part of a hydrogen atom of the group or All of them may be substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group, an ethyl fluorenyl group or a phenyl group. R111 is a linear chain having 1 to 8 carbon atoms. a branched or substituted alkyl, alkenyl or alkoxyalkyl group, a phenyl group, or a naphthyl group, a part or all of one or more of the hydrogen atoms of the groups may further be an alkyl or alkane having 1 to 4 carbon atoms. An oxy group; a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an ethyl fluorenyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom. Here, the aspect of the aryl group of R11G may, for example, be a 1,2-phenylene group or a 1,8-naphthylene group, and the olefin group may, for example, be a methylene group, an ethylene group, a trimethylene group or a tetra group. Methylene, phenylethylene, norbornane-2,3-diyl, etc., in terms of subchain flammability, 1,2-vinylidene, 1 phenyl-l,2-vinylidene Base, 5-northene-2,3-diyl, and the like. The alkyl group of R111 is the same as R1GIa~ phase-27-(25) 1282908, and the alkenyl group may, for example, be a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group or a 3-butene group. Base, iso-pentadienyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexene , 1-pentenyl, 3-pentenyl, 6-pentenyl, 7-octenyl, etc., alkoxyalkyl, methoxymethyl, ethoxymethyl, propoxymethyl, butyl Oxymethyl, pentoxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, Methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, A Oxyhexyl, methoxyheptyl and the like. Further, the alkyl group having 1 to 4 carbon atoms which may be further substituted may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl propyl group, a n-butyl group, an isobutyl group or a tertiary butyl group. The alkoxy group having 1 to 4 carbon atoms may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group or a tertiary butoxy group. The phenyl group which may be substituted by an alkyl group, an alkoxy group, a nitro group or an ethyl fluorenyl group having 1 to 4 carbon atoms may, for example, be a phenyl group, a tolyl group, a p-tertiary butoxyphenyl group or a p-ethenebenzene group. Examples of the heterocyclic aromatic group having 3 to 5 carbon atoms include a pyridyl group and a furyl group. Specifically, for example, tetramethylammonium trifluoromethane methanesulfonate, tetramethylammonium nonafluorobutane phthalate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, Tetramethylammonium tosylate, diphenyl iodide trifluoromethanesulfonate, fluoromethane methanesulfonic acid (p-tert-butoxyphenyl) phenyl iodine gun, p-toluene diphenyl iodine iron, P-toluenesulfonic acid (p-tert-butoxyphenyl)phenyl wart, triphenylmethanesulfonate triphenylsulfonium, trifluoromethane methanesulfonic acid (for tertiary -28-(26) 1282908~? Difluoromethane methanesulfonic acid bis(p-tertiary butoxybutoxyphenyl)diphenylfluorene-fluorine machine ten^one gas methane methanesulfonic acid tris(p-tert-butoxyphenylphenyl)phenyl鎏, difluoromethyl hydrazine) 鎏, p-toluene ortho-triphenyl sulfonium, p-toluene sulfonic acid (p-tert-butoxyphenyl) diphenyl _, Xiao (four) bis (nitroxy s phenyl) benzene ® 某 某 苯基 苯基 鎏 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九 九Sanjiao production office, one methyl hydrazine, = fluoromethane, acid expansion ring Hexyl group (2_oxanthene, p-toluenesulfonic acid dimethyl-gold)

Cyclohexyl)_, p-toluene acid extension cyclohexylmethyl (2. oxycyclohexyl) fluorene, trifluoromethyl methacrylate, dimethylphenyl hydrazine, dimethyl hydrazine, trifluoromethyl hydrazine Acid dicyclohexylphenyl fluorene, p-toluic acid dicyclohexyl phenyl fluorene, trinaphthyl trifluoromethanesulfonate, trifluoromethane methanesulfonic acid (2-n-decyl) methyl (2-oxy ring) Hexyl) bismuth, ethylene bis [methyl(2-oxycyclopentanyl) fluorene compound, salt of I, 2,-naphthylcarbonylmethyltetrahydrothiophene trifluoromethanesulfonate and the like.

Bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazide, bis(xylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, double Cyclopentasulfonyl) diazocarbazide, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazide, bis(dibutylsulfonyl)diazo A hospital, bis (n-propyl sulphate) diazocarbazone, bis(isopropylsulfonyl)diazomethane, bis(tertiary butylsulfonyl)diazomethane, bis(n-pentanyl) Sulfhydryl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(secondary pentaalkylsulfonyl)diazomethane, bis(tripentylsulfonylsulfonyl)diazo Methane, 1-cyclohexylsulfonyl-bu (tertiary butylsulfonyl)diazomethane, I-cyclohexylsulfonyl-1-(-29-(27) 1282908 trispentanesulfonyl a diazomethane derivative such as diazomethane, 1 -tridecylsulfonyl-1 -(tert-butylsulfonyl)diazomethane. Double-0-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-0-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-indole-(p-toluene)醯)) α-dicyclohexylethylenediazine, bis--0-(p-toluenesulfonyl)-2,3-pentanedione ethanedioxime, bis-indole-(p-toluenesulfonyl)-2- Methyl-3,4-pentanedione ethanedioxime, bis-indole-(n-butanesulfonyl)-α-dimethylglyoxime, bis- 0-(n-butanesulfonyl)-α -diphenylglyoxime, bis-indole-(p-toluenesulfonyl)-α-dicyclohexylethylenedifluoride, bis-indole-(p-toluenesulfonyl)-2,3-pentanedione Bismuth, bis-indole-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione Ethyl 2-oxo, bis-indole-(Zhengdingyuan sulfonyl) 1-methylidene Bismuth, bis-indole (n-butanesulfonyl)-α-diphenylglyoxime, bis--0-(n-butanesulfonyl)_α-dicyclohexylethanediamine, bis-indole-( n-Butane dilatyl)-2,3·pentanedione ethanedioxime, bis-indole-(n-butanesulfonyl)-2-methyl-3,4-pentanedione ethanedioxime, bis- 〇-(methanesulfonyl)-α-dimethylglyoxime, bis-0-(trifluoromethanesulfonyl)-α-dimethylglyoxime, double-0-(1,1 1-trifluoroethanesulfonyl)-"-dimethylglyoxime, bis--0-(-tertiary butylsulfonyl)-α-dimethylglyoxime, bis-indole (full Fluoxane sulfonyl)-α-dimethylglyoxime, bis-indolyl-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-indole-(phenylsulfonyl)- α-Dimethylglyoxime, bis-O-(p-fluorophenylsulfonyl)dimethylglyoxime, bis-indole-(p-tert-butylphenylsulfonyl)-α-dimethyl ethane , bis-indole-(xylsulfonyl)-α-dimethylglyoxime, bis-indole-(camphorsulfonyl)-α-dimethylglyoxime and the like. 30- 1282908 (28) bisnaphthylsulfonyl methane, bistrifluoromethanesulfonylmethane methane methane, bisethylsulfonyl methane, bispropylsulfonylpropylsulfonyl methane, di-p-toluene a bis-derivative derivative of sulfhydrylmethane, bisbenzene, etc. 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, benzyl-2-(p-toluenesulfonyl)propane, etc. a nitrobenzyl sulfonate derivative of 2,6-dinitrobenzyl, p-toluenesulfonic acid 2, etc. 1,2,3-tris(methanesulfonyloxy)benzene, 1 ,2,3- Trisulphonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxysulfonate derivative. N-hydroxysuccinimide, mercaptomethane methanesulfonate, N-imine Trifluoromethane methanesulfonate, N-hydroxy amber sulfonate, N-hydroxy amber succinimide decyl 1-propane sulfonate succinimide fluorenyl 2-propane sulfonate, N-hydroxy amber 1 Pentane sulfonate, N-hydroxy succinimide fluorenyl 1-octyl N-hydroxy amber succinimide fluorenyl p-toluene sulfonate, N-hydroxy decyl, p-methoxybenzene sulfonate, N -hydroxyammonia oxime oxime sulfonate, N-hydroxy succinimide, fluorenyl benzene sulfonate, peryleneimine fluorenyl-2,4,6-trimethyl sulfonate, N-hydroxysuccinyl 1 -naphthalenesulfonate, N-hydroxysuccinimide, fluorenyl 2-naphthylhydroxy-2-phenylsuccinimide, mercaptomethane methanesulfonate, enediminoimide methane methanesulfonate, N-hydroxyl Maleic acid ester, N-hydroxy-2-phenyl maleimide imide methane, dimethylsulfone, bisisosulfonyl methane 2-isopropylcarbonyl. , 4-dinitrobenzyl (trifluoromethyl) benzene, etc. • Acryl mercapto ethane ester, N-hydroxy quinone iminyl alkane sulfonate, amber ruthenium amide - atmosphere, N-carbyl succinimide oxime sulfonate, NN-hydroxy cis-butylenimine ethane sulfonate, N- -31 - (29) 1282908 hydroxypentamethylene imide methane methane sulfonate , N-hydroxypentadienyl benzene sulfonate, N-hydroxy quinone methane methane sulfonate, N-hydroxy quinone benzene sulfonate, N-hydroxy quinone imine trifluoromethane Sulfonic acid ester, N-hydroxy quinone imine p-toluenesulfonate, N-hydroxy (L) dimethyl sulfoximine methane methane sulfonate, N-hydroxy (L) dimethyl sulfonium benzene sulfonate, N-hydroxy-5-nordecene-2,3-dicarboxyindolimethane methanesulfonate, N-hydroxy-5-northene-2,3-dicarboxylimine imine trifluoromethane methanesulfonic acid a sulfonate derivative of an N-hydroxyquinone imine compound such as an ester, N-hydroxy-5-northene-2,3-dicarboxylimenide p-toluenesulfonate or the like. Triphenylsulfonium trifluoromethane methanesulfonate, trifluoromethane methanesulfonic acid (p-tert-butoxyphenyl)diphenylphosphonium, trifluoromethanesulfonic acid tris(p-tert-butoxyphenyl)phosphonium , triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl)diphenylphosphonium, p-toluenesulfonic acid tris(p-tert-butoxyphenyl)phosphonium, trifluoromethane Trinaphthylsulfonate, cyclohexylmethyl (2-oxocyclohexyl)phosphonium trifluoromethanesulfonate, (2-n-decyl)methyl(2-oxocyclohexyl)phosphonium trifluoromethane methanesulfonate Key salt of 1,2'-naphthylcarbonylmethyltetrahydrothiophene thiophenium trifluoromethanesulfonate, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazo Methane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(2-butylsulfonyl) Diazo of diazomethane methane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane Methane derivative, double- 0-( p-Tolylsulfonyl) dimethylglyoxime, bis-indole-(n-butanesulfonyl)-α-dimethylglyoxime, etc., bis-naphthylsulfonyl methane, etc. Bismuth derivative, hydrazine-hydroxy-32-(30) 1282908-based amber quinone iminyl methane methanesulfonate, N-hydroxy amber succinimide fluorenyl trifluoromethane methane sulfonate, N-hydroxy amber醯iminodecyl 1-propane sulfonate, N-hydroxysuccinimide fluorenyl 2-propane sulfonate, N-hydroxy amber succinimide decyl 1-pentane sulfonate, N-hydroxy amber oxime N-hydroxy quinone imine such as imindolyl p-toluenesulfonate, N-hydroxy (L) dimethyl sulfoximine methane mesylate, N-hydroxy (L) dimethyl sulfoxide The sulfonate derivative of the compound can be suitably used. Further, the above acid generators may be used alone or in combination of two or more. The amount of the acid generator to be added is preferably from 1 to 50 parts, more preferably from 0.5 to 40 parts, per 100 parts by weight of the base polymer. When the amount is less than 0.1 part, the amount of acid generated is small, and the crosslinking reaction is insufficient. When the amount exceeds 50 parts, mixed image formation due to movement of the acid to the upper photoresist film may occur. Further, the film material under the present invention can be blended with an alkaline compound for improving storage stability. In the case of the basic compound, the acid generated in a trace amount from the acid generator is used for preventing the crosslinking reaction, and is suitable for a compound useful for the acid quencher. The basic compound may, for example, be a primary, secondary or tertiary aliphatic amine, a mixed amine, an aromatic amine, a heterocyclic amine, a nitrogen-containing compound having a carboxyl group, or a sulfonyl group. A nitrogen-containing compound, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcohol-containing nitrogen-containing compound, a guanamine derivative, a quinone imide derivative, or the like. Specifically, g, the first stage of the aliphatic amines, may be exemplified by ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tri-33· (31) 1282908 Butane, pentylamine, tertiary pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, decylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, Examples of the ethylenediamine, tetraethyleneamine, and the like, and the secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, and - secondary butylamine, diamylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, diamine, diamine, two dodecylamine, two sixteen Amine, N,N-dimethylmethylenediamine, ν, Ν·dimethylethylenediamine, hydrazine, hydrazine dimethyltetraethylene ethylamine, etc., tertiary aliphatic amines, Examples of trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, three secondary butylamines, triamylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine , triheptylamine, trioctylamine, tridecylamine, tridecylamine, Dodecylamine, three hexadecylamine, hydrazine, hydrazine, Ν', Ν'-tetramethylmethylenediamine, hydrazine, hydrazine, hydrazine , Ν'-tetramethylethylenediamine, hydrazine, hydrazine , hydrazine, hydrazine, - tetramethyltetraethylene ethylamine, and the like. Further, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, calamine, phenethylamine, and dimethylamine. Specific examples of the aromatic amines and the heterocyclic amines include aniline derivatives (for example, aniline, N-toluidine, oxime-ethylaniline, guanidine propyl aniline, hydrazine, hydrazine-dimethylaniline, 2-toluidine, 3-toluidine, 4-toluidine, ethylaniline, propylaniline, trimethylamine, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2, 6-dinitroaniline, 3,5-dinitroaniline, hydrazine, hydrazine-dimethyl-o-toluidine, etc.), diphenyl (p-toluene) amine, methyl diphenylamine, triphenylamine, phenylene Diamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2 Η-pyrrole, 1 ·methylpyrrole, 2,4-dipyrrole, -34-1282908 (32) 2,5 - one A D-pyrrol, n-methylpyrrolidone, etc.), vaginal derivatives (such as stagnation, stagnation, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4-methylpyrimidine) Squatting, 4-methyl-2-phenylimidazole, etc., pyrazidin derivatives, furazan derivatives, pyroline derivatives (eg oxaporphyrin, 2-methyl-1 -pyrroline, etc.) Pyrrolidine derivatives (eg pyridinium) Pyridine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolium derivatives, pyridine derivatives (eg pyridine, mepyridyl, ethylpyridine, propylpyridine, butyl) Pyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tributylpyridine, two Phenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, [-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine , 2-(i-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), anthracene derivatives, pyridine derivatives, pyridinium derivatives, pyrazoline derivatives, pyrazole derivatives, piperazine Pyridine derivatives, piperene derivatives, morpholine derivatives, anthracene derivatives, isoindole derivatives, 1 carbazole derivatives, porphyrin derivatives, D-quinoline derivatives (eg quinoline, 3-quinoline) Carbonitrile, etc., isoquinoline derivatives, porphyrin derivatives, oxazoline derivatives, _ morphine derivatives, oxazine derivatives, hydrazine derivatives , pteridine derivatives, carbazole derivatives, phenidine derivatives, acridine derivatives, morphine derivatives, 1,1 〇-orthophenone derivatives, adenine derivatives, adenosine derivatives, guanine derivatives , guanosine derivatives, uracil derivatives, uridine derivatives, and the like. Further, in the case of the nitrogen-containing compound having a carboxyl group, for example, an aminobenzoic acid, an anthracenecarboxylic acid, or an amino acid derivative (for example, nicotinic acid, propylamine-35-(33) 1282908 acid, arginine, Aspartic acid, glutamic acid, aglyconic acid, histidine, isoleucine, glycosaminoglycine, leucine, methionine, phenylalanine, threonine (threonine) ), lysine, 3-aminopyridin-2-carboxylic acid, methoxyalanine, etc., in the case of a nitrogen-containing compound having a sulfonyl group, 3 · pyridine sulfonic acid, p-toluene sulfonic acid pyridine In the case of a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, or an alcohol-containing nitrogen-containing compound, 2-hydroxypyridine, amino-cresol, 2,4-quinolinediol, and 3 may be exemplified. - hydrazine methanol hydroxide, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-Aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4 ·(2-hydroxyethyl) morpholine, 2 _(2-hydroxyethyl)pyridine, 1 - (2-hydroxyethyl Piperidin, 1-[2-(2-hydroxyethoxy)ethyl]pipepene, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)- 2-pyrrolidone, 3-hexahydropyridyl-1,2-propanediol, 3-N-pyrrolidinyl-1,2-propanediol, 8-hydroxyluronidine, 3-decane nucleoside, 3•tropanal, 1-methyl-2-0 ratio D-ethanol 1-aziridine ethanol, N-(2-hydroxyethyl) quinone imine, N-( 2 -Hydroxyethyl)isonicotinamide and the like. As the guanamine derivative, for example, formamide, N-methylformamide, hydrazine, hydrazine dimethylformamide, acetamide, N-methylacetamide, hydrazine, hydrazine-dimethyl group can be exemplified. Acetamide, acetamide, benzamide, and the like. In the case of the quinone imine derivative, the compounding amount of the basic compound such as quinone imine, amber imine, maleimide or the like can be exemplified, and it is 0,001 to 2 parts based on 100 parts of the total base polymer. Especially 0.01 to 1 part is appropriate. When the compounding amount is less than 0.001 parts, the mixing effect is not good. When more than 2 parts are used, 1282908 (34) The acid generated by the heat is completely trapped and cannot be crosslinked. The organic solvent which can be used in the film forming material of the present invention is not particularly limited as long as it can dissolve the underlayer polymer, acid oxidizing agent, crosslinking agent, and other additives. Specific examples thereof include ketones such as cyclohexanone and methyl-2-pentanone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, and 1-methoxy Alcohols such as benzyl-2-propanol and 1-ethoxy-2-propanol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, two Ethers such as ethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3 - esters of ethyl ethoxypropionate, tertiary butyl acetate, tertiary butyl propionate, propylene glycol monomethyl ether acetate, propylene glycol monoterpene butyl-ether acetate, etc. One type or two or more types are used, but are not limited thereto. In the present invention, among these organic solvents, diethylene glycol dimethyl ether or ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether acetate, and the like may be suitably used. The amount of the solvent is preferably from 50,000 to 1 〇 5 〇 based on 1 part of the total base polymer, particularly preferably from 1,000 to 5,000. The underlayer film 'under the present invention is the same as the photoresist, and can be formed on a substrate to be processed by a spin coating method or the like. After the spin coating, the solvent is evaporated, and it is desirable to bake in order to prevent mixing with the photoresist upper layer and to promote the crosslinking reaction. The baking temperature is in the range of 80 to 300 ° C, and can be suitably used within the range of 10 to 3 sec. Further, the thickness of the underlayer film can be suitably selected, but it is preferably 100 to 20,000 nm, particularly 150 to 1 5,000 nm. After the underlayer film is formed, a photoresist layer is formed thereon. -37- (35) 1282908 At this time, a conventional one can be used for forming the photoresist composition for the photoresist layer. In terms of oxygen gas etching resistance, the base polymer is a ruthenium-containing polymer such as a polyfluorenated sesquioxane derivative or a vinyl decane derivative, and an organic solvent or an acid generator can be used, which can be used as needed. A positive resistive composition such as a basic compound or the like is used. Further, as the polymer containing a ruthenium atom, such a conventional polymer used for a photoresist composition can be used. In the case where the photoresist layer is formed of the above-mentioned photoresist composition, as in the case of forming the underlayer film described above, the spin coating method can be suitably used. After the photoresist is spin-coated, prebaking may be performed, but it is preferably carried out at a temperature of 80 to 180 ° C for 10 to 300 seconds. Thereafter, exposure is performed in the field of the multilayer photoresist film pattern according to a conventional method, and post-exposure baking (PEB) and development are performed to obtain a photoresist pattern. Further, the thickness of the photoresist film is not particularly limited. It is preferably 30 to 500 nm, especially 50 to 400 nm. Next, the obtained photoresist pattern is used as a mask to carry out uranium engraving mainly composed of oxygen gas. This etching can be carried out in accordance with a conventional method. At this time, it is also possible to add an inert gas such as oxygen gas, He, or Ar, or CO, CO 2 , NH, SO, N, or N02 gas. In particular, the latter gas is used for sidewall protection of the pattern sidewalls for undercutting (u n d e r c u t ). Next, etching of the substrate to be processed can be carried out according to a conventional method. For example, when the substrate is SiO 2 or SiN, the fluorocarbon-based gas is mainly used for etching, and P_Si or A and W are etched mainly by a chlorine-based or bromine-based gas. The underlayer film of the present invention is characterized in that the substrate to be processed is excellent in etching resistance. Further, in terms of the substrate to be processed, it can be formed on the substrate. The substrate-38-(36) 1282908 is not particularly limited, and Si, α-Si, P-Si, SiO 2 , SiN, SiON, W, TiN, A1, etc. may be used differently from the film to be processed (substrate to be processed). Material. As the film to be processed, various Low-K films such as Si, SiO, SiON, SiN, p-Si, a-Si, W, W-Si, Al, Cu, Al-Si, and their stopper films can be used, and usually A thickness of 50 to 1 0,000 nm, especially 100 to 5,000 nm is formed. [Embodiment] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Polymerization Examples, Examples and Comparative Examples, but the present invention is not limited thereto. [Synthesis Example 1] Adding force to a flask of 300 mL □ 1-naphthol I449g (l mole), trifluoromethanesulfonic acid O.Olg, stirring at 50 ° C while p-cyclopentadiene i 3 29g (1 Mo Ear) drip for 1 hour. After stirring at the same temperature for 1 hour, the temperature was raised to 150 ° C, and the mixture was stirred for 2 hours to complete the reaction. The unreacted product was distilled off under reduced pressure, dissolved in 200 g of 1,2-dichloroethane, and the catalyst and metal impurities were removed by washing with water, and 1,2-dichloroethane was removed under reduced pressure to obtain 2 30 g of polymer-1. The molecular weight (Mw) in terms of styrene, the degree of dispersion (Mw/Mn) was determined by gel permeation chromatography G PC, and the ratio of naphthol to pentacyclopentadiene in the polymer was analyzed by 1H-NMR. The following way is obtained. Polymer 1; naphthol: Cyclopentadiene (Mole Ratio) = 〇.55: 〇·45 Mw 4,400, Mw/Mn3.1 -39- 1282908 (37) [Synthesis Example 2] In 300 mL The flask was charged with 144 g of 1-naphthol (1 mol), ruthenium trifluoromethanesulfonate (7 g), and 66 g of p-cyclopentadiene (〇. 5 mol) was dropped for 1 hour while stirring at 50 t. After stirring at the same temperature for one hour, the temperature was raised to 15 (TC), and the mixture was stirred for two hours to complete the reaction. The unreacted product was distilled off under reduced pressure, dissolved in 200 g of 1,2-dichloroethane, and washed with water. The catalyst and the metal impurities were removed, and 1,2-dichloroethane was removed under reduced pressure to obtain 180 g of polymer-2. The molecular weight (Mw), the degree of dispersion (Mw/Mn) was determined by GPC, and was determined by 1 Η-N MR analysis determined the ratio of naphthol to pentacyclopentadiene in the polymer in the following manner: Polymer 2; 1-naphthol: Cyclopentadiene (Morby) = 0.77: 023 Mw5, 2 00 5 Mw/Mn2.8 [Synthesis Example 3] In a 300 mL flask, 7-methoxy-1-naphthol 174 g (1 mol) of trifluoromethanesulfonic acid 0.007 g was added, and the mixture was stirred at 50 ° C while being doubled. 66 g (0.5 mol) of cyclopentadiene was dropped for 1 hour, and after stirring at the same temperature for one hour, the temperature was raised to 150 ° C, and the mixture was stirred for two hours to complete the reaction. The unreacted material was distilled off under reduced pressure. Dissolved in 200 g of 1,2-dichloroethane, the catalyst and metal impurities were removed by washing with water, and 1,2-dichloroethane was removed under reduced pressure to obtain 221 g of polymer-3. By GPC The molecular weight (Mw), the degree of dispersion (Mw/Mn) (38) 1282908, and the ratio of naphthol to pentocyclopentadiene in the polymer were determined by 1 H-NMR analysis in the following manner. 7-Methoxy 1 naphthol: Cyclopentadiene (Morby) = 0.77: 0.23

Mw 3,200, Mw/Mn2.6 [Synthesis Example 4] In a 500 mL flask, 1 mL of cyclohexane was obtained, and 1 to naphthol/cyclopentadiene phenolic enamel resin l〇〇g obtained in Synthesis Example 1 was 5 g of tetramethylammonium bromide was dissolved, and 3 g of epichlorohydrin was dropped, stirred at 80 ° C for 1 hour to carry out an addition reaction, 8 g of sodium hydroxide was added, and a ring closure reaction was carried out at 80 ° C for 3 hours. An epoxy compound is obtained. Thereafter, unreacted epichlorohydrin and sodium hydroxide were removed by washing with water, and ethyl acetate was removed by drying under reduced pressure to obtain 1 22 g of a glycidyl group-substituted 1-naphthol/penecyclopentadienyl phenol hydrazide. Paint resin. The molecular weight (Mw), the degree of dispersion (Mw/Mn) were determined by G PC, and the ratio of the epoxypropyl-substituted naphthol to the cyclopentadiene in the polymer was determined by 1 Η-NMR analysis in the following manner. . Polymer 4; epoxypropyl substituted 1 naphthol: cyclopentadiene (mole ratio) = 0.55: 0.45

Mw6, 100, Mw/Mn3.1, [Examples, Comparative Examples] Naphthol-penecyclopentadiene represented by polymers 1 to 4, acid generator represented by AG1, 2, CR 1,2 The cross-linking agent was dissolved in a solvent containing 0. 1% by weight of FC-430 (manufactured by Sumitomo (39) 1282908 3 Μ) as shown in Table 1, to a fluorine content of 0 · 1 / m The resin filter was filtered to separately prepare the underlayer film solution. In the case of the polymer used in the comparative example, a cresol novolac lacquer resin between M w 8,900 and M w/Mn4.8 was used, and in the comparative polymer-2, Mw 3,300, Mw/ was used. 1-naphthol resin of Mn3.5, Comparative Example Polymer-3 used Mw3 3,000, Mw/Mnl.9 p-hydroxystyrene: hydroxyethyl acrylate 3 0/70 (mole ratio).

A solution of the underlayer film forming material is applied onto a ruthenium substrate, and baked at 200 ° C for 60 seconds to form a film having a film thickness of 400 nm (hereinafter referred to as UDL 1 to 7 for short), and JA Woollam's variable angle of incident angle is obtained. The refractive index (η, k ) of UDL 1 to 7 in the wavelength i93 nm was determined by an ellipsometer (VASE), and the results are shown in Table 1.

-42- (40) 1282908 Table 1

No. Polymer (parts by weight) Crosslinking agent (parts by weight) Acid generator (parts by weight) Solvent (parts by weight) Wavelength 193 mm Medium refractive index n値k値UDL1 Polymer 1 (28.0) CR1 (10) AG1 ( 5) PGMEA (1〇〇) 1.67 0.20 UDL2 Polymer 2 (28.0) CR1 (1〇) AG1 (5) PGMEA (100) 1.61 0.25 UDL3 Polymer 3 (28.0) CR1 (10) AG1 (5) PGMEA (100) ) 1.69 0.24 UDL4 Polymer 4 (10.0) Polymer 1 (18.0) - AG1 (5) PGMEA (100) 1.68 0.20 UDL5 Polymer 1 (18.0) Comparative Polymer 3 (10.0) CR1 (10) AG1 (5) PGMEA (100) 1.69 0.22 UDL6 Polymer 1 (28.0) CR2 (10) AG1 (5) PGMEA (100) 1.67 0.21 UDL7 Polymer 1 (28.0) CR1 (10) AG2 (5) PGMEA (100) 1.67 0.19 Comparative Example 1 Comparative Polymer 1 (25.0) CR1 (10) AG1 (5) PGMEA (100) 1.32 0.62 Comparative Example 2 Comparative Polymer 2 (28.0) CR1 (10) AG1 (5) PGMEA (100) 1.40 0.33 Comparative Example 3 Comparative Polymerization 3 (22.0) CR1 (10) AG1 (5) PGMEA (100) 1.70 0.25 PGMEA; propylene glycol monomethyl ether acetate (41) 1282908

AG2

N eight N Ο〆 Μ

〇, 'CRl

CK2

Next, a solution of the underlayer film forming material was applied onto a SiO 2 substrate having a thickness of 300 nm, and baked at 20 (TC for 60 seconds to form a film having a thickness of 400 nm (hereinafter, abbreviated as UDL 1 to 7). The composition shown modulates the ruthenium-containing polymer _1, 2, the acid generator PAG1, the alkali additive AACN, and the solvent is used to form a ruthenium-containing photoresist 1 for ArF. The photoresist is applied to the above-mentioned underlayer films UDL1 to 7. Bake at 110 ° C for 60 seconds to form a ruthenium-containing photoresist film having a film thickness of 200 nm. Next, an ArF exposure apparatus (manufactured by Nikon Corporation; S 305 B, NA 0.68, σ θ.85, 2/3 wheel) Body illumination, CR mask), exposed, and baked at 1 l ° ° C for 90 seconds (ΡΕΒ ) with 2.38 wt% aqueous solution of tetramethylammonium hydroxy (TMAH) to obtain a positive pattern. Observe the resulting pattern图.1〇RmL/S has a pattern shape, and the folded edge is not formed in the vicinity of the substrate shown in Table 3. The pattern of the rectangle is confirmed by the mixing phenomenon. Next, the dry etching resistance test is performed. First, the underlayer film (UDL 1 to 7) is formed in the same manner as the above-mentioned refractive index - 44-1282908 (42), and the underlayer film is formed. The uranium engraving test of CHFs/CF4 gas was tested under the following condition (i). In this case, the film thickness of the film and photoresist under and after etching was measured using a dry uranium engraving apparatus TE-8 5 OOP manufactured by Tokyo Electron Co., Ltd. The results are shown in Table 4. The CHF 3 / CF 4 system gas worms! 1 test worms ij conditions are as follows. Chamber pressure 40.0Pa RF power 1 3 00 W gap 9mm CHF3 gas flow 30ml / Min CF4 gas flow rate 30 ml/min Ar gas flow rate 1 00 ml/min Time 60 seconds Further, the above-mentioned underlayer film (UDL1 to 7) was used, and the etching test of the C12/BC13-based gas was carried out under the following condition (2). The film thickness difference of the polymer film before and after etching was determined using a dry etching apparatus L-5 07D-L manufactured by Nippon Anelva Co., Ltd. The results are shown in Table 5. The uranium etching test etching conditions of the C12/BC13 system gas are as follows. The chamber pressure is 40.0Pa RF power 3 00W Clearance 9 mm C I2 gas flow 30ml/min BC 13 gas flow 30ml/min - 45- (43) 1282908 CH F3 Gas flow rate l〇〇ml/min 〇2 gas flow 2ml/min time 60 seconds On the one hand, after the above ArF exposure and development, O.lOpmL/S The type of tantalum-containing photoresist is etched by oxygen gas. The etching conditions are as follows: chamber pressure 450 mTorr RF power 600 W Ar gas flow 40 sccm 〇 2 gas flow 60 sccm gap 9 mm time 2 0 seconds Next, at (1) The CHF3/CF4 gas was etched under the conditions shown, and the SiO 2 substrate was processed. After the development of the oxygen gas, the pattern profile of the CHF3/CF4 gas after the etching of the substrate was observed by an electron microscope (S - 4 7 0 0 ) manufactured by Hitachi, Ltd., and the shape was compared and summarized in Table 3. . After the development, the cross-sectional shape of the tantalum-containing photoresist was observed, and the cross-sectional shape of the underlying film was observed after etching with CHF3/CF4 after oxygen etching -46- (44) 1282908 Table 2

No. Polymer (parts by weight) Acid generator (parts by weight) Base (parts by weight) Solvent (parts by weight) Photoresist 1 ArF ytterbium-containing polymer 1 (100) PAG1 (2.2) AACN (〇.3) PGMEA (1,200 ) Photoresist 2 ArF germanium containing polymer 2 (100) PAG1 (2.2) AACN (0.3) PGMEA (800)

(including ArF sand polymer-1) (including ArF sand polymer-2) (a=0.40, b=0.50, c=0.1 Mw=8,800) (d=0.30, e=0.70 Mw=2,500)

47 1282908 (45) Table 3

No. After image pattern shape Oxygen gas etched shape CF4/CHF3 Gas etched shape UDL1 Vertical shape Vertical shape Vertical shape UDL2 Vertical shape Vertical shape Vertical shape UDL3 Vertical shape Vertical shape Vertical shape UDL4 Vertical shape Vertical shape Vertical shape UDL5 Vertical Shape Vertical shape Vertical shape UDL6 Vertical shape Vertical shape Vertical shape UDL7 Vertical shape Vertical shape Vertical shape Comparative example 1 Pattern collapse Comparative example 2 Undercut shape, side wall roughness due to standing wave Conical shape Conical shape Comparative example 3 Vertical Shape Vertical Shape Conical Shape and Film Thinning -48-1282908 Table 4 Antireflection Film, Photoresist No. CHF3/CF4 System Gas Uranium [J Speed (nm/min) UDL 1 92 UDL2 95 UDL3 99 UDL4 90 UDL5 103 UDL6 92 UDL7 93 Comparative Example 1 98 Comparative Example 2 95 Comparative Example 3 144 -49- 1282908 (47) Table 5 Antireflection film, photoresist No. C12/BC13 system gas etching rate (nm/min) UDL1 118 UDL2 120 UDL3 122 UDL4 123 UDL5 126 UDL6 110 UDL7 133 Comparative Example 1 125 Comparative Example 2 118 Comparative Example 3 166 As shown in Table 1 Under the invention, the refractive index of the film is η 1 1.5 to 1.9, and k 値 is in the range of 0.15 to 0.3. The film thickness of 200 nm or more can exert the optimum refractive index (η ) and extinction of the antireflection effect as much as possible. The coefficient (k), as shown in Tables 4 and 5, is also etched at the same rate as the phenolic enamel resin in the CF4/CHF3 gas and the C12/BC13 gas, and is etched in comparison with the polyhydroxystyrene hydroxyethyl acrylate copolymer. Low speed and high uranium tolerance. Further, as shown in Table 3, the shape of the photoresist after development was confirmed, and after the oxygen etching, the shape of the underlayer film after the substrate was processed and etched was also good. -50- 1282908 (48) [Effect of the invention] The underlayer forming material of the present invention has a refractive index n 値 in the range of i · 5 to i · 9, k 値 in the range of 0.1 5 to 0.3 'above 2 〇〇 _ In order to exhibit only a sufficient antireflection effect, the CFWCHF3 gas and the C12/BC13 gas used for substrate processing are also etched at the same rate as the phenolic enamel resin, and have high etching resistance. Moreover, the shape of the photoresist after patterning is also good. [Simplified Explanation of the Drawing] [Fig. 1] is a graph showing the relationship between the film thickness of the antireflection film and the reflectance. [Fig. 2] A graph showing the relationship between the film thickness of the underlayer film and the reflectance under the range in which the refractive index k 下 of the underlayer film is fixed at 0.3 and the range of η 値 is changed from 1 · G to 2 · 0. [Fig. 3] The relationship between the film thickness and the reflectance of the underlayer film under the range of 0.1 to 1.0, and the underlying film yield η値 is fixed at 1.5.

Claims (1)

1282908 (1) Pickup, Patent Application No. 1 · A pattern forming method, characterized in that a photoresist underlayer film containing a cocondensate of a naphthol derivative and a cyclopentadiene as an antireflection film is suitable for being processed On the substrate, a layer of a photoresist composition is applied on the underlayer film, radiation is irradiated in the field of the pattern circuit, and a photoresist pattern is formed by developing a liquid image to form a photoresist layer by a dry etching device. A processor that performs the underlayer and the substrate to be processed. 2. The method for forming a pattern according to claim 1, wherein the photoresist composition contains a polymer containing a ruthenium atom, and the photoresist layer is used as a mask for dry etching of the underlayer film, and oxygen gas is used. The etching gas of the main body is performed. 3. The method of forming a pattern according to the second aspect of the patent application, wherein the underlying film is formed into a reticle and the substrate processing system is subjected to dry etching after the oxygen cooked body is inscribed. 4) An underlayer film forming material characterized by a photoresist underlayer film forming material used in the pattern forming method of claim 1 '2 or 3, wherein a naphthol derivative and a cyclopentadiene are co-produced. The condensate is represented by the following general formula (1) or (2), -52- 1282908 (2) wherein R1 to R8 are independently a hydrogen atom, a thiol group, a substitutable alkyl group having 1 to 6 carbon atoms, a substitutable alkoxy group having 1 to 6 carbon atoms, a substitutable alkoxycarboxy group having 2 to 6 carbon atoms, a substitutable aryl group having 6 to 10 carbon atoms, a phenylene group having a carbon number of 1 to 6, an isocyanate group or an epoxy group, m , η is a positive integer). 5 · As in the scope of patent application, under the fourth paragraph, the film forming material μ 八 ’ 吏 a ' organic solvent, cross-linking agent and acid generator. -53-