Metal-containing resist underlayer film forming composition containing polyoxometalate

Photoresist underlayer film forming composition containing metal containing polyacid

Metal-containing resist underlayer film forming composition containing polyoxometalate

The present invention relates to a composition used for an underlayer film formed between a substrate used in manufacturing a semiconductor device and a photoresist (for example, light irradiation photoresist, electron beam photoresist, EUV photoresist).

In the past, in the manufacture of semiconductor devices, micro-processing was mostly carried out by lithography etching technology that uses light to irradiate a photoresist. The aforementioned microfabrication involves forming a light-irradiating photoresist film on a semiconductor substrate such as a silicon wafer, and irradiating active light such as ultraviolet rays through a mask pattern depicting the pattern of the semiconductor device on it, developing, and irradiating the resulting light The photoresist pattern is used as a protective film for the substrate to be etched, and the substrate surface is formed with a processing method that corresponds to the aforementioned pattern to form fine concavities and convexities. However, in recent years, with the increasing integration of semiconductor devices, the active light used has also tended to be shorter wavelengths from KrF excimer lasers (248nm) to ArF excimer lasers (193nm). Along with this, the influence of active light reflected by the semiconductor substrate will cause great problems. Therefore, the use of hard masks The multi-layer photoresist process of the mask is used for photolithographic etching.

For photoresist underlayer films containing metals other than silicon, it has been disclosed to use metal alkoxides such as tungsten, zinc, aluminum, indium, etc., mixed with silicon alkoxides and hydrolyzed to be used as inorganic films for multilayer photoresist processes. (Patent Document 1).

In addition, it is also disclosed that a metal oxide film containing a single metal such as zirconium, molybdenum, and hafnium, metal oxyacids, metal oxides, metal hydroxides, metal alkoxides, metal halides, and metal oxyhalides ( Patent Document 2).

In addition, it is also disclosed that it contains water-soluble methyl tungstate, and at least one selected from anionic polymers, nonionic polymers, anionic surfactants, and nonionic surfactants containing tertiary amine groups A composition for forming a tungsten oxide film as an additive (Patent Document 3).

In addition, there is also disclosed a pattern forming method in which a polysiloxane composition is used to form a silicon-containing film on the upper side of the substrate to be processed, and an acid, an alkali, a metal complex compound, a metal chloride compound, and an onium chloride compound are added at the same time. Among them, the acid is hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide acid, perchloric acid, hydrogen peroxide, carbonic acid, formic acid, acetic acid, benzenesulfonic acid, phosphoric acid, heteropoly acid, inorganic solid acid, etc. (Patent Document 4 ).

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2012-215877

[Patent Document 2] JP 2013-023407

[Patent Document 3] JP 2013-040993

[Patent Document 4] JP 2013-083963

<p>The object of the present invention is to provide a thin film (underlayer film) forming composition used together with photoresist (light irradiation photoresist, electron beam photoresist, EUV photoresist) in the photolithographic etching step in the manufacture of semiconductor devices. Specifically, the present invention provides a photoresist underlayer film forming composition for lithography etching that forms a photoresist underlayer film that can be used as a hard mask. Furthermore, a photoresist underlayer film forming composition for lithography etching for forming a photoresist underlayer film that can be used as an anti-reflection film is provided. In addition, there is provided a photoresist underlayer film for lithography etching that does not cause intermixing with the photoresist and has a higher dry etching speed than the photoresist, and a photoresist underlayer film forming composition for forming the underlayer film Things.</p><p>In addition, the objective is to provide an underlayer film (hard mask) for EUV photoresist, which is a thin film underneath the EUV photoresist, and an underlayer film forming composition for solvent development photoresist. It is more desirable to provide an invention of reverse material.</p>

<p>In the present invention, the first point of view is a photoresist underlayer film forming composition containing component (A): isopoly acid or heteropoly acid or a salt of these, or a combination of these Combined with (B) component: polysiloxane, polyhafnium oxide or zirconium oxide or a combination of these, and based on the total measurement of the (A) component and the (B) component, the (A) component is A photoresist underlayer film forming composition containing 0.1 to 85% by mass, characterized in that the polysiloxane has the following formula (1): [Chemical1]R¹_aR²_bSi(R³)_4-(a+b) Formula (1) (where R¹It is an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a sulfhydryl group or a cyano group, and is a Si-C Bonded to silicon atom, R²It is a ring containing a nitrogen atom or an organic group containing it, a condensed aromatic ring or an organic group containing it, a protected phenolic hydroxyl group or an organic group containing it, or a biaryl group or an organic group containing it, and is For Si-C bonding and silicon atom bonding, R³It is an alkoxy group, an oxy group, or a halogen group, a is an integer from 0 to 3, b is an integer from 0 to 3, (a+b) is an integer from 0 to 3) The hydrolyzable silane hydrolysis condensate , The hydrolyzable silane with (a+b) being 0 in the formula (1) contains 60 to 85 mol% in the fully hydrolyzable silane, and the multi-hafnium oxide is the formula (2): [Chemical2]Hf(R⁴)₄ Formula (2) (R⁴Is a hydrolysis condensate of hydrolyzable hafnium represented by an alkoxy group, an acyloxy group, or a halogen group), the zirconium oxide is the formula (3) or the formula (4): [Chemical3]Zr(R⁵)₄ Formula (3) </p><p>ZrO(R⁶)₂ Formula (4) (R⁵, R⁶Respectively, they are hydrolyzable zirconium represented by alkoxy group, acyloxy group, halogen group, or nitrate ion) or the hydrolysis condensate of a combination of these.</p><p>The second aspect is the photoresist underlayer film forming composition described in the first aspect, wherein the isopolyacid is an oxo acid of tungsten, molybdenum, or vanadium, or a salt of these.</p><p>The third aspect is the photoresist underlayer film forming composition described in the first aspect, wherein the isopolyacid is methyl tungstic acid or methyl ammonium tungstate.</p><p>The fourth aspect is the photoresist underlayer film forming composition described in the first aspect, wherein the heteropoly acid is an oxyacid of tungsten, molybdenum, or vanadium, or a salt of these, and an oxyacid of silicon or phosphorus, Or a combination of these salts.</p><p>The fifth aspect is the photoresist underlayer film forming composition described in the first aspect, wherein the heteropoly acid is silicotungstic acid, phosphotungstic acid, or phosphomolybdic acid.</p><p>The sixth viewpoint is that the photoresist underlayer film forming composition described in any one of the first to fifth viewpoints further contains an acid.</p><p>The seventh viewpoint is that the photoresist underlayer film forming composition described in any one of the first to sixth viewpoints still contains water.</p><p>The eighth aspect is a photoresist underlayer film characterized by coating the photoresist underlayer film forming composition described in any one of the first to seventh aspects on a semiconductor substrate and sintering it.</p><p>A ninth aspect is a method of manufacturing a semiconductor device, which is characterized by comprising: coating the photoresist underlayer film forming composition described in any one of the first to seventh aspects on a semiconductor substrate, and then sintering it to form The step of forming a photoresist underlayer film, the step of coating a photoresist composition on the aforementioned photoresist underlayer film to form a photoresist film, the step of exposing the aforementioned photoresist film, and the photoresist film development after exposure. The step of photoresist patterning, the step of etching the photoresist underlayer film through the photoresist pattern, and the step of processing the semiconductor substrate through the patterned photoresist underlayer film.</p><p>And the tenth viewpoint is a method of manufacturing a semiconductor device, characterized by comprising: forming an organic underlayer film on a semiconductor substrate, and forming the photoresist underlayer film described in any one of the first to seventh viewpoints The step of coating the composition on it and sintering to form a photoresist underlayer film, the step of coating the photoresist composition on the aforementioned photoresist underlayer film to form a photoresist film, and exposing the aforementioned photoresist film Step: After exposure, the photoresist film is developed to obtain the photoresist pattern, the photoresist underlayer film is etched by the photoresist pattern, and the organic underlayer film is etched by the patterned photoresist underlayer film , And the step of processing the semiconductor substrate by patterning the organic underlayer film.</p>

<p>The present invention is that using the photoresist underlayer film forming composition of the present invention, the above-mentioned thin film (underlayer film) can be formed on a substrate by a coating method, or an organic underlayer film on the substrate can be interposed on the substrate by a coating method The above-mentioned film is formed, and then a photoresist film (for example, light irradiation photoresist, electron beam photoresist, EUV photoresist) is formed on the film. Subsequently, a photoresist pattern is formed through exposure and development. The photoresist pattern is used to perform dry etching on the above-mentioned film to transfer the pattern, and the substrate is processed by the pattern, or by etching the organic underlayer film Inventions such as processing the substrate through an organic underlayer film with a transfer pattern.</p><p>In addition to forming fine patterns, there is a tendency to thin the thickness of the photoresist film in order to prevent the pattern from collapsing. Therefore, after the photoresist is thinned, it is generally dry etching for pattern transfer of the film that exists in the lower layer. If the etching speed is not higher than the etching rate of the upper layer film, the pattern transfer cannot be performed. .</p><p>The present invention is that the organic underlayer film is interposed on the substrate, or the organic underlayer film is not interposed, the film obtained from the composition of the present invention is sequentially coated thereon, and then a photoresist film (organic photoresist film ).</p><p>Among them, the film of organic components and the film of inorganic components will cause a great difference in the dry etching speed depending on the etching gas selection method. The film of organic components can increase the dry etching speed with oxygen gas, and the film of inorganic components In a halogen-containing gas, the dry etching speed can be increased.</p><p>Since the photoresist underlayer film forming composition of the present invention is a film of inorganic components, it can be used to form photoresist patterns and dry-etch the film of the present invention existing in the lower layer by using halogen-containing gas to transfer the pattern. Printed on thin Film, use halogen-containing gas, and process the substrate with the pattern transferred on the film. Or use a film with a pattern transferred, dry etching the underlying organic underlayer film with oxygen gas to transfer the pattern on the organic underlayer film, use the organic underlayer film with the pattern transferred, use The halogen-containing gas processes the substrate and so on.</p><p>In addition, the photoresist underlayer film obtained from the photoresist underlayer film forming composition of the present invention has an extremely sufficient hard mask function as an anti-reflection function.</p><p>In addition, the photoresist underlayer film of the present invention as an inorganic polymer (interlayer film) is extremely effective for etching of an organic underlayer film existing thereunder, or as a hard mask during substrate processing (etching). That is, those having sufficient dry etching resistance to the oxygen-based dry etching gas of the organic underlayer film during substrate processing or.</p><p>Therefore, the thin film obtained from the photoresist underlayer film forming composition of the present invention has the ability to increase the dry etching speed for the upper layer photoresist and the dry etching resistance during substrate processing.</p><p>In addition, the above-mentioned film forming composition of the present invention can be used as a non-intermixing with EUV photoresist and can prevent poor exposure light during EUV exposure, such as those generated by the substrate or interface of the above-mentioned UV or DUV. The EUV photoresist lower layer anti-reflection film that reflects the light. The EUV photoresist lower layer film. When the resulting film is used as the lower layer of EUV photoresist, it can effectively prevent reflection.</p><p>In addition, the photoresist underlayer film forming composition of the present invention can be used as a reverse material when a solvent that does not dissolve the photoresist is selected. When used as a reverse material, first of all, the present invention The photoresist underlayer film forming composition covers the photoresist pattern formed on the substrate, and is dried to form a thin film. Subsequently, the formed film is etched back to expose the photoresist pattern surface, and then dry etching is performed with a gas (for example, oxygen-based gas) that can selectively remove the photoresist, so that only the film layer remains The way to reverse the pattern.</p><heading level="1">[The form of implementing the invention]</heading><p>The present invention is a photoresist underlayer film forming composition, which contains (A) component: isopoly acid or heteropoly acid or a salt of these, or a combination of these, and (B) component: polysiloxane, polysiloxane Hafnium oxide or zirconium oxide or a combination of these, based on the total amount of (A) component and (B) component, (A) component is a photoresist underlayer film forming composition containing 0.1 to 85% by mass, which It is characterized in that the polysiloxane is a hydrolyzable condensate of hydrolyzable silane represented by the following formula (1), and the hydrolyzable silane in which (a+b) is 0 in the formula (1) is contained in the fully hydrolyzable silane 60 to 85 mol%, the multi-hafnium oxide is a hydrolyzable condensate of hydrolyzable hafnium represented by formula (2), and the zirconia is hydrolyzable zirconium represented by formula (3) or formula (4), or a combination of these The hydrolysis condensate.</p><p>The isopolyacid used in the component (A) of the present invention is an oxo acid of tungsten, molybdenum, or vanadium, or a salt of these. As the salt, alkali metals (Na, K, Li) can be used, and ammonium salt is preferred. Ammonium salt, for example, ammonium (NH₄), primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium, etc. These organic groups can be, for example, alkyl groups with 1 to 4 carbon atoms. Among them, ammonium (NH₄) Is better.</p><p>Isopolyacids, for example, methyl tungstic acid, methyl molybdic acid, methyl vanadic acid, methyl ammonium tungstate, methyl ammonium molybdate, methyl ammonium vanadate, etc. are exemplified.</p><p>The heteropoly acid used in the component (A) is an oxo acid of tungsten, molybdenum, or vanadium, or a combination of these salts, and an oxo acid of silicon or phosphorus, or a combination of these salts. As the salt, alkali metals (Na, K, Li) can be used, and ammonium salt is preferred. Ammonium salt, for example, ammonium (NH₄), primary ammonium, secondary ammonium, tertiary ammonium, quaternary ammonium, etc. These organic groups can be, for example, alkyl groups with 1 to 4 carbon atoms. Among them, ammonium (NH₄) Is better.</p><p>Heteropolyacids, for example, silicotungstic acid, silicomolybdic acid, silicovanadic acid, phosphotungstic acid, phosphomolybdic acid, phosphovanadic acid, ammonium silicotungstate, ammonium silicomolybdate, ammonium silicovanadate, ammonium phosphotungstate, Ammonium phosphomolybdate, ammonium phosphovanadate, etc.</p><p>The polysiloxane used in component (B) is a hydrolyzable condensate (polysiloxane) of hydrolyzable silane represented by formula (1), where (a+b) in formula (1) is hydrolyzable with 0 Silane can contain 60 to 85 mol% in fully hydrolyzable silane.</p><p>In formula (1), R¹Among the alkyl groups, for example, straight-chain or branched alkyl groups with 1 to 10 carbon atoms, etc., for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- Butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1, 1-Dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl , 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n -Butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl -n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl Group, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl -N-propyl and 1-ethyl-2-methyl-n-propyl, etc.</p><p>In addition, the alkyl group may also be a cyclic alkyl group, for example, a cyclic alkyl group having 1 to 10 carbon atoms, for example, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl -Cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2, 3-Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3 -Methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3 -Dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-di Methyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl , 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2- Methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, etc.</p><p>The aryl group includes aryl groups having 6 to 20 carbon atoms, for example, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chloro Phenyl, p-chlorophenyl, o-fluorophenyl, p-sulfanylphenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyano Phenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl , 2-Finyl, 3-Finyl, 4-Finyl and 9-Finyl, etc.</p><p>Examples of alkenyl groups include alkenyl groups having 2 to 10 carbon atoms, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, and 2-butene. Group, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl- 2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propyl vinyl, 1-methyl-1-butenyl, 1 -Methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl Alkenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1 -Dimethyl-2-propenyl, 1-i-propyl vinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentene Group, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl -1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2 -Methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl- 2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3 -Ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4- Pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2- Dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylvinyl, 1, 3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-i-butylvinyl, 2 ,2-Dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3 -Butenyl, 2-i-propyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1- Ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2 -Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-t-butylvinyl, 1-methyl-1-ethyl- 2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-i-propyl-1-propenyl, 1-i -Propyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl- 2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylidene-ring Pentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl , 3-methyl-5-cyclopentenyl, 3-methylidene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.</p><p>In addition, halogenated alkyl groups and halogenated aryl groups include, for example, organic groups substituted with halogen atoms such as fluorine, chlorine, bromine, or iodine among the above groups.</p><p>Examples of the organic group having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl.</p><p>The organic group having an acrylic group includes, for example, acrylic methyl, acrylic ethyl, and acrylic propyl.</p><p>Examples of the organic group having a methacrylic acid group include methacrylic acid methyl group, methacrylic acid ethyl group, and methacrylic acid propyl group.</p><p>Organic groups with hydrogen sulfide groups, for example, ethyl hydrogen sulfide Group, butyl hydrosulfide, hexyl hydrosulfide, octyl hydrosulfide, etc.</p><p>Examples of the organic group having an amino group include aminomethyl, aminoethyl, and aminopropyl.</p><p>Examples of the organic group having a cyano group include cyanoethyl and cyanopropyl.</p><p>Examples of the organic group having a sulfonyl group include methylsulfonyl group, allylsulfonyl group, and phenylsulfonyl group.</p><p>R²The ring containing a nitrogen atom or the organic group containing it in, for example, the organic group represented by formula (5), etc.,<chemistry general="n"><img file="TWI646153B_D0001.tif" he="483" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="957" /></chemistry>In formula (5), R⁷Represents a hydrogen atom, or an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or an organic group containing these, R⁸Represents an alkylene group, hydroxyalkylene group, thioether group, ether group, ester group, or a combination of these with 1 to 10 carbon atoms, X₁Express formula (5), formula (6) or formula (7):<chemistry general="n"><img file="TWI646153B_D0002.tif" he="627" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1394" /></chemistry>In formula (6), formula (7), and formula (8), R⁹To R¹³Each represents a hydrogen atom, or an alkyl group, alkenyl group, epoxy group, sulfonyl group with 1 to 10 carbon atoms, or These organic groups can be Si-C bonding and bonding with silicon atoms.</p><p>The above R²The ring containing the nitrogen atom or the organic group containing the nitrogen atom may be an imidazole group or an organic group containing an imidazole group.</p><p>Also, the above R²The condensed aromatic ring group or the organic group containing it can be naphthyl or anthracenyl.</p><p>R²The protected phenolic hydroxyl group or the organic group containing it may be an alkoxyalkyl substituted aryl group or an alkoxyalkoxyalkyl substituted aryl group. When a protected phenolic hydroxyl group is used, the appearance profile of the photoresist can be improved by increasing the acidity. Among them, the alkyl part and alkoxy part of these organic groups can be, for example, the alkyl groups and alkoxy groups exemplified above or below.</p><p>Again, R²Examples of the diaryl group or the organic group containing it include diphenyl group.</p><p>The above R⁷To R¹³Among the alkyl groups, aryl groups, alkenyl groups, halogenated alkyl groups, halogenated aryl groups, organic groups with epoxy groups, organic groups with acrylic groups, organic groups with methacrylic groups, and hydrogen sulfide groups The organic group, the organic group having an amine group, the organic group having a cyano group, and the organic group having a sulfonyl group can be, for example, the content exemplified in the above examples.</p><p>The above R³In the alkoxy group, for example, a carbon number of 1 to 30, more preferably a carbon number of 1 to 10, etc., such as methoxy, ethoxy, n-propoxy, i-propoxy , N-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy Oxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl- n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl Base-n- Pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-di Methyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy , 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n -Propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, phenoxy, etc.</p><p>The above R³Examples of the anooxy group include those having 1 to 30 carbon atoms, and more preferably those having 1 to 10 carbon atoms, for example, methylcarbonyloxy, ethylcarbonyloxy, and n-propylcarbonyloxy. , I-propylcarbonyloxy, cyclopropylcarbonyloxy, n-butylcarbonyloxy, i-butylcarbonyloxy, s-butylcarbonyloxy, t-butylcarbonyloxy, cyclobutyl Carbonyloxy, 1-methyl-cyclopropylcarbonyloxy, 2-methyl-cyclopropylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl- n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, cyclopentylcarbonyloxy, 1-methyl-ring Butylcarbonyloxy, 2-methyl-cyclobutylcarbonyloxy, 3-methyl-cyclobutylcarbonyloxy, 1,2-dimethyl-cyclopropylcarbonyloxy, 2,3-di Methyl-cyclopropylcarbonyloxy, 1-ethyl-cyclopropylcarbonyloxy, 2-ethyl-cyclopropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentyl Carbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl -n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n -Butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl- n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy Group, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n- Propylcarbonyloxy, cyclohexylcarbonyloxy, 1-methyl-cyclopentylcarbonyloxy, 2-methyl-cyclopentylcarbonyloxy, 3-methyl-cyclopentylcarbonyloxy, 1- Ethyl-cyclobutylcarbonyloxy, 2-ethyl-cyclobutylcarbonyloxy, 3-ethyl-cyclobutylcarbonyloxy, 1,2-dimethyl-cyclobutylcarbonyloxy, 1 ,3-Dimethyl-cyclobutylcarbonyloxy, 2,2-dimethyl-cyclobutylcarbonyloxy, 2,3-dimethyl-cyclobutylcarbonyloxy, 2,4-dimethyl Group-cyclobutylcarbonyloxy, 3,3-dimethyl-cyclobutylcarbonyloxy, 1-n-propyl-cyclopropylcarbonyloxy, 2-n-propyl-cyclopropylcarbonyloxy Group, 1-i-propyl-cyclopropylcarbonyloxy, 2-i-propyl-cyclopropylcarbonyloxy, 1,2,2-trimethyl-cyclopropylcarbonyloxy, 1,2 ,3-Trimethyl-cyclopropylcarbonyloxy, 2,2,3-trimethyl-cyclopropylcarbonyloxy, 1-ethyl-2-methyl-cyclopropylcarbonyloxy, 2- Ethyl-1-methyl-cyclopropylcarbonyloxy, 2-ethyl-2-methyl-cyclopropylcarbonyloxy, 2-ethyl-3-methyl-cyclopropylcarbonyloxy and the like.</p><p>The above R³Examples of the halogen group include fluoro, chloro, bromo, and iodo.</p><p>The hafnium polyoxide used in the present invention includes, for example, a hydrolysis condensate of the hydrolyzable hafnium represented by formula (2) and the like.</p><p>R in formula (2)⁴, Can be for example with R in formula (1)³An example of the same.</p><p>The zirconium oxide used in the present invention includes, for example, the hydrolyzable zirconium hydrolysis condensate represented by formula (3), formula (4) or a combination of these Wait.</p><p>In formula (3) and formula (4), R⁵And R⁶Is the R in formula (1)³An example of the same. R⁵And R⁶More exemplified are nitrate ions.</p><p>In the present invention, the compounds represented by formula (1), formula (2), formula (3), and formula (4) of polysiloxane, polyhafnium oxide, or zirconia precursor used as component (B) , The hydrolysis condensate obtained by hydrolysis alone or in combination can be mixed with component (A), or the compound represented by formula (1), formula (2), formula (3), and formula (4) can be combined separately It can be hydrolyzed singly or in combination, and it can coexist with component (A) at this time.</p><p>In the hydrolysis condensate (polymer, copolymer) used in the present invention, the component (B) alone or the combination of the component (A) and the component (B) may be as exemplified below.</p><p><chemistry general="n"><img file="TWI646153B_D0003.tif" he="2185" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1768" /></chemistry></p><p><chemistry general="n"><img file="TWI646153B_D0004.tif" he="1738" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="2000" /></chemistry></p><p>The above-mentioned hydrolysis condensate is a polymer, or a copolymer, and can be a condensate with a weight average molecular weight of 300 to 1,000,000, 300 to 100,000, or 300 to 20,000. These molecular weights are the molecular weights obtained by conversion of polystyrene using GPC analysis. GPC measurement conditions, for example, use GPC device (trade name HLC-8220GPC, manufactured by Tosoh Co., Ltd.), GPC column (trade name ShodexKF803L, KF802, KF801, manufactured by Showa Denko), column temperature of 40°C, and eluent The (elution solvent) is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml/min, and the standard sample is polystyrene (manufactured by Showa Denko Co., Ltd.).</p><p>Hydrolysis of alkoxysilyl, oxysilyl or silyl halide In each hydrolyzable group, 1 mol, 0.5 to 100 mol, preferably 1 to 10 mol of water is used.</p><p>In addition, for each hydrolyzable group 1 mol, 0.001 to 10 mol, preferably 0.001 to 1 mol of hydrolysis catalyst is used.</p><p>In the case of hydrolysis and condensation, the reaction temperature is usually 20 to 120°C or less.</p><p>The hydrolysis can be complete hydrolysis or partial hydrolysis. That is, the hydrolyzate or monomer may remain in the hydrolysis condensate. That is, the above-mentioned hydrolysis condensate may contain a compound represented by formula (1), formula (2), formula (3), or formula (4), or these hydrolyzates may also be included.</p><p>In the case of hydrolysis and condensation, a catalyst can be used.</p><p>Examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.</p><p>As a metal chelate compound as a hydrolysis catalyst, for example, triethoxy. Mono (acetylpyruvate) zirconium, three-n-propoxy. Mono (acetylpyruvate) zirconium, tri-i-propoxy. Mono (acetylpyruvate) zirconium, three-n-butoxy. Mono (acetylpyruvate) zirconium, three-sec-butoxy. Mono (acetylpyruvate) zirconium, three-t-butoxy. Single (acetylpyruvate) zirconium, diethoxy. Bis (acetylpyruvate) zirconium, two-n-propoxy. Bis (acetylpyruvate) zirconium, two-i-propoxy. Bis (acetylpyruvate) zirconium, two-n-butoxy. Bis (acetylpyruvate) zirconium, two-sec-butoxy. Bis (acetylpyruvate) zirconium, two-t-butoxy. Bis (acetylpyruvate) zirconium, monoethoxy. Participation (acetylpyruvate) zirconium, mono-n-propoxy. Ginseng (B Acetopyruvate) zirconium, mono-i-propoxy. Participation (acetylpyruvate) zirconium, mono-n-butoxy. Participation (acetyl pyruvate) zirconium, single-sec-butoxy. Participation (acetyl pyruvate) zirconium, mono-t-butoxy. Ginseng (acetyl pyruvate) zirconium, four (acetyl pyruvate) zirconium, triethoxy. Mono (ethyl acetyl acetate) zirconium, tri-n-propoxy. Mono (ethyl acetyl acetate) zirconium, tri-i-propoxy. Mono (ethyl acetyl acetate) zirconium, tri-n-butoxy. Mono (ethyl acetyl acetate) zirconium, three-sec-butoxy. Mono (ethyl acetyl acetate) zirconium, three-t-butoxy. Mono (ethyl acetyl acetate) zirconium, diethoxy. Bis (ethyl acetyl acetate) zirconium, two-n-propoxy. Bis (ethyl acetyl acetate) zirconium, di-i-propoxy. Bis (ethyl acetyl acetate) zirconium, two-n-butoxy. Bis (ethyl acetyl acetate) zirconium, two-sec-butoxy. Bis (ethyl acetyl acetate) zirconium, two-t-butoxy. Bis (ethyl acetyl acetate) zirconium, monoethoxy. Ginseng (ethyl acetyl acetate) zirconium, mono-n-propoxy. Ginseng (ethyl acetyl acetate) zirconium, mono-i-propoxy. Ginseng (ethyl acetyl acetate) zirconium, mono-n-butoxy. Ginseng (ethyl acetyl acetate) zirconium, mono-sec-butoxy. Participation (Ethyl Acetate) Zirconium, Mono-t-Butoxy. Ginseng (Ethyl Acetate) Zirconium, Tetra (Ethyl Acetate) Zirconium, Mono (Acetyl Pyruvate) Ginseng (Ethyl Acetate) Zirconium, Bis (Acetyl Acetate) Pyruvate) bis(ethyl acetylacetate) zirconium, ginseng (acetyl pyruvate) mono(ethyl acetylacetate) zirconium, and other zirconium chelate compounds; ginseng (acetyl acetone) Ester) aluminum, ginseng (ethyl acetate) aluminum and other aluminum chelate compounds; etc.</p><p>Organic acids as hydrolysis catalysts, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, decanoic acid, grass Acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, eicosatetraenoic acid, skikimic acid, 2-ethyl Caproic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, two Chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.</p><p>As the inorganic acid as a hydrolysis catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.</p><p>Organic bases as hydrolysis catalysts, for example, pyridine, pyrrole, piperazine, pyrrolazine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine , Triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, etc. Inorganic bases, for example, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these can be used singly or in combination of two or more.</p><p>Organic solvents used for hydrolysis, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane , N-octane, i-octane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n -Propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-pentylnaphthalene, trimethylbenzene and other aromatic hydrocarbons System solvent; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec- Butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2- Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2 ,6-Dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexane Monoalcohol solvents such as alcohol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzyl alcohol, diacetone alcohol, cresol, 4-methyl-2-pentanol, etc.; ethylene glycol, Propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethyl Polyol solvents such as hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; acetone, methyl ethyl ketone, methyl-n-acetone, methyl- n-butanone, diethyl ketone, methyl-i-butanone, methyl-n-pentanone, ethyl-n-butanone, methyl-n-hexanone, di-i-butanone, trimethyl Ketone solvents such as ylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; diethyl ether, i-propyl ether, n- Butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyl two Oxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethyl Glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether , Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Alcohol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and other ether solvents; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, acetic acid n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetylacetate, Acetyl ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate acetate, diethylene glycol mono-n-butyl acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate , Ethyl propionate, n-butyl propionate, i-pentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Ester solvents such as pentyl ester, diethyl malonate, dimethyl phthalate, and diethyl phthalate; N-methylformamide, N,N-dimethylformamide, N,N -Diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc. Solvents; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutane, 1,3-propane sultone, etc. These solvents can be used 1 type or a combination of 2 or more types.</p><p>Among them, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Alcohol monopropyl ether acetate is preferred.</p><p>In addition, ketones such as acetone or non-alcoholic polar solvents such as tetrahydrofuran are also suitable for use when using hydrolyzable silane (silicone with 2 to 3 hydrolyzable groups in the molecule of the silane during hydrolysis) as a raw material. Better. However, silanes with 5 to 9 hydrolyzable groups in the molecule of the hydrolyzable silane are likely to be gelled due to excessive hydrolysis and condensation reactions in the aforementioned acetone solvent.</p><p>(B) Hydrolyzable organosilanes of component (B), the hydrolysis condensate (polymer, copolymer) obtained by using a catalyst in the solvent, or without using a catalyst for hydrolysis and condensation, can use vacuum distillation to remove by-products at the same time The alcohol, or the hydrolysis catalyst or water used. In addition, the acid or alkali catalyst used in the hydrolysis can be removed by means of neutralization or ion exchange. Therefore, in the photoresist underlayer film forming composition used in the photolithographic etching step of the present invention, an acid (organic acid), Salt, water, alcohol, or a combination of these.</p><p>The above-mentioned organic acids, for example, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, salicylic acid Sour etc. Among them, oxalic acid, maleic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, hexenoic acid, fumaric acid, Phenylacetic acid, phenylpropionic acid, triphenylacetic acid, cinnamic acid, benzoic acid, trimellitic acid, pyromellitic acid, etc. are preferred. In addition, the amount of the organic acid is 0.5 to 5.0 parts by mass relative to 100 parts by mass of the (B) component. In addition, pure water, ultrapure water, ion-exchange water, etc. can be used as water, and the addition of The amount is 1 to 20 parts by mass relative to 100 parts by mass of the photoresist underlayer film forming composition.</p><p>The photoresist underlayer film forming composition of the present invention may contain a salt. The salt has a function as a hardening catalyst when the coating film containing the condensate (polyorganosiloxane, copolymer, or a combination of these) is heated and hardened.</p><p>As the salt, for example, ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used. The addition amount of the above-mentioned salt is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass relative to 100 parts by mass of component (B).</p><p>The photoresist underlayer film forming composition for lithographic etching of the present invention may contain organic polymer compounds, photoacid generators, surfactants, etc., if necessary, in addition to the above-mentioned components.</p><p>When an organic polymer compound is used, the dry etching speed (reduction of film thickness per unit time), attenuation coefficient and refraction of the photoresist underlayer film formed by the photoresist underlayer film forming composition for lithographic etching of the present invention can be adjusted Rate etc.</p><p>The organic polymer compound is not particularly limited, and various organic polymers can be used. For example, condensation polymerization polymers and addition polymerization polymers can be used. For example, polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol-novolac, naphthol-novolac, polyether, polyamide, polycarbonate, etc. Addition polymerization polymer and condensation polymerization polymer. In addition, benzene ring, naphthalene ring, anthracene ring, three<img file="TWI646153B_D0005.tif" wi="66" he="70" img-format="tif" img-content="character" orientation="portrait" inline="no" />Organic polymers with aromatic ring structures such as ring, quinoline ring, and quinoxaline ring. Again The organic polymer compound, for example, may include benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, and anthryl methyl methacrylate contained in the form of structural units. Addition polymerized polymer obtained by addition polymerizable monomers such as methyl acrylate, styrene, hydroxystyrene, benzyl vinyl ether and N-phenylmaleimide, or phenol-novolak and naphthol-phenol Varnish and other polycondensation polymers.</p><p>When an addition polymerized polymer is used as an organic polymer compound, the polymer compound may be a homopolymer or a copolymer. In the production of addition polymerizable polymers, addition polymerizable monomers are used. Examples of these addition polymerizable monomers include acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, and maleic compounds. Amide compounds, maleic anhydride, acrylonitrile, etc.</p><p>In addition, when the organic polymer compound contains a hydroxyl group, the hydroxyl group can form a crosslinking reaction with the polyorganosiloxane of the component (B).</p><p>As the organic polymer compound, a polymer compound having a weight average molecular weight of 1,000 to 1,000,000, or 3,000 to 300,000, or 5,000 to 200,000, or 10,000 to 100,000 can be used.</p><p>In the case of using an organic polymer compound, the ratio is 1 to 200 parts by mass, or 5 to 100 parts by mass, or 10 to 50 parts by mass, or 20 to 30 parts by mass relative to 100 parts by mass of component (B).</p><p>The photoresist underlayer film forming composition of the present invention may contain an acid generator.</p><p>The acid generator includes, for example, a thermal acid generator or a photo acid generator.</p><p>Photoacid generator, which can generate acid during photoresist exposure. Therefore, the acidity of the underlying film can be adjusted. This point is one of the methods to match the acidity of the lower film with the acidity of the upper photoresist. In addition, by adjusting the acidity of the lower layer film, the pattern shape of the photoresist formed on the upper layer can also be adjusted.</p><p>The photoacid generator contained in the photoresist underlayer film forming composition of the present invention includes, for example, an onium chloride compound, an amoximine compound, and a disulfonyldiazomethane compound.</p><p>Onium chloride compounds, for example, diphenyl iodonium hexafluorophosphate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium nonafluoro n-butane sulfonate, diphenyl iodonium perfluoro-n-octane sulfonic acid Ester, diphenyl iodophor camphorsulfonate, bis(4-tert-butylphenyl) iodophorsulfonate and bis(4-tert-butylphenyl) iodotrifluoromethanesulfonate and other iodochloride compounds , And triphenyl sulfonium hexafluoroantimony ester, triphenyl sulfonium nonafluoro n-butane sulfonate, triphenyl sulfonium camphor sulfonate and triphenyl sulfonium trifluoromethane sulfonate, etc.</p><p>Sulfonimide compounds, for example, N-(trifluoromethanesulfonyloxy) succinimide, N-(nonafluoron-butanesulfonyloxy) succinimide, N-(camphorsulfonyloxy) ) Succinimidyl and N-(trifluoromethanesulfonyloxy) naphthalenedimethimide, etc.</p><p>Disulfonyl diazomethane compounds, for example, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, double (p-toluenesulfonyl) diazomethane, bis(2,4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane, etc.</p><p>Only one kind of photoacid generator can be used, or two or more kinds can be used in combination Both can be used together.</p><p>In the case of using a photoacid generator, the ratio is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass relative to 100 parts by mass of component (B).</p><p>Surfactants are effective for suppressing the occurrence of sand holes and lines when the photoresist underlayer film forming composition for lithographic etching of the present invention is applied to the substrate.</p><p>In addition, to the photoresist underlayer film forming composition of the present invention, a rheology modifier, an adhesion auxiliary agent, etc. can be added. The rheology modifier is effective for improving the fluidity of the photoresist underlayer film forming composition. Adhesive supplements are effective for improving the adhesion between semiconductor substrates or photoresist and thin films.</p><p>The solvent used in the photoresist underlayer film forming composition of the present invention is not particularly limited as long as it can dissolve the aforementioned solid components, and can be used arbitrarily. These solvents, for example, methanol, ethanol, propanol, isopropanol, butanol, 4-methyl-2-pentanol, methyl cellosolve (cellosolve) acetate, ethyl cellosolve (cellosolve) Acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate , Toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl glycolate Ester, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Methyl propionate, methyl pyruvate, propyl Ethyl ketoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl Ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate Ester, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isoamyl formate, methyl acetate, ethyl acetate, pentyl acetate, isoamyl acetate, N-butyl acetate, i-butyl acetate, sec-butyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, propionic acid Isobutyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, 2-hydroxy-2-methylpropane Ethyl acrylate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3- Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyl ester, methyl acetylacetate , Toluene, xylene, methyl ethyl ketone, methyl acetone, methyl butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N, N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, methyl isobutyl carbinol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more kinds.</p><p>Hereinafter, the use of the photoresist underlayer film forming composition of the present invention will be explained.</p><p>Substrates used in the manufacture of semiconductor devices (for example, silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant materials (low dielectric constant) -k material) coated substrate, etc.), use a suitable coating method such as a spin coater, a strip coater, etc., to coat the photoresist underlayer film forming composition of the present invention, and then form a photoresist underlayer film through sintering . The sintering conditions can be appropriately selected from the sintering temperature of 80 to 500°C, or 80 to 250°C, and the sintering time of 0.3 to 60 minutes. Preferably, the sintering temperature is 150° C. to 500° C., and the sintering time is 0.5 to 2 minutes. Wherein, the thickness of the formed underlayer film is, for example, 10 to 1000 nm, preferably 20 to 500 nm, more preferably 50 to 300 nm, most preferably 100 to 200 nm, particularly preferably 10 to 100 nm.</p><p>Secondly, on the formed photoresist underlayer film, a layer of light irradiating the photoresist is formed. The light-irradiated photoresist layer can be formed by a well-known method, that is, it can be coated and sintered on the underlayer film of the photoresist composition solution irradiated with light. The film thickness of the photoresist for light irradiation is, for example, 50 to 10000 nm, preferably 100 to 2000 nm, more preferably 200 to 1000 nm, most preferably 30 to 200 nm.</p><p>According to the present invention, an organic underlayer film can be formed on a substrate according to necessity, and then, the photoresist underlayer film of the present invention can be formed on the organic underlayer film or the substrate, and then the photoresist is coated with light to irradiate the photoresist. In this step, when covering a thin light-irradiating photoresist from the viewpoint of preventing the pattern width of the light-irradiated photoresist from narrowing and pattern collapse, it is also possible to select an appropriate etching gas to perform the process on the substrate. Processing. For example, when using a fluorine-based gas that has a very fast etching speed on the photoresist by light irradiation as the etching gas, the photoresist underlayer film of the present invention can be processed, and the photoresist underlayer film of the present invention can be used to have an extremely fast etching speed. When the oxygen-based gas is used as the etching gas, the organic underlayer film can also be processed. In addition, when the fluorine-based gas with a very fast etching rate for the organic underlayer film is used as the etching gas, the substrate can also be processed.</p><p>The light irradiating photoresist formed on the photoresist underlayer film of the present invention is not particularly limited as long as the light used for exposure can be sensed. It can use either of a negative light irradiating photoresist and a positive light irradiating photoresist. For example, a positive light-irradiation photoresist formed by a novolak resin and 1,2-naphthoquinone diazide sulfonate, a binder having a base that is decomposed by an acid to increase the rate of alkali dissolution, and a photoacid generator The formed chemically amplified light-irradiation photoresist, the low-molecular-weight compound that is decomposed by acid to increase the alkali dissolution rate of the light-irradiated photoresist, the chemically amplified light The binder that decomposes the base to increase the alkali dissolution rate, the low-molecular compound that decomposes through acid and increases the alkali dissolution rate of the photoresist, and the chemically amplified photoresist formed by the photoacid generator. For example, the product name APEX-E manufactured by CHYPRE, the product name PAR710 manufactured by Sumitomo Chemical Industry Co., Ltd., and the product name SEPR430 manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000) The fluorine atom-containing polymer described is a photoresist for light irradiation, etc.</p><p>Secondly, exposure is performed through a specific mask. Exposure can use KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) and F2 excimer laser (wavelength 157nm), etc. After exposure, post-exposure heating (postexposurebake) can also be performed according to necessity. The post-exposure heating can be carried out under appropriate selection conditions between the heating temperature of 70°C to 150°C and the heating time of 0.3 to 10 minutes.</p><p>Furthermore, in the present invention, a photoresist for electron lithography etching can be used as a photoresist instead of a light irradiation photoresist, or an EUV photoresist can be used. The electron line photoresist can use either negative type or positive type. For example, a chemically amplified photoresist formed by a binder that has a base that is decomposed by an acid generator and an acid to change the rate of alkali dissolution, and has a chemically amplified photoresist that is decomposed by an alkali-soluble binder and an acid generator and acid to make light A chemically amplified photoresist formed by a low-molecular-weight compound whose alkali dissolution rate changes, and a binder that has a base that is decomposed by acid generators and acids, and changes the alkali dissolution rate, and decomposes photoresist by acid. A chemically amplified photoresist formed by a low-molecular compound whose alkali dissolution rate changes, and a non-chemically amplified photoresist formed by a binder that is decomposed by electron rays to change the alkali dissolution rate. Non-chemically amplified photoresist, etc. formed by the adhesive at the part where the alkali dissolution rate is changed by cutting. In the case of using these electron beam photoresist, the photoresist pattern can be formed in the same way as the case where the irradiation source is the photoresist using electron beam light.</p><p>In addition, as EUV photoresist, a methacrylate resin photoresist can be used.</p><p>Secondly, use a developer for development. According to this method, for example In the case of using positive light to irradiate the photoresist, the light irradiating photoresist can be removed from the exposed part to form a pattern of light irradiating the photoresist.</p><p>Developers, for example, aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc., ethanolamine, Alkaline aqueous solutions such as amine aqueous solutions such as propylamine and ethylenediamine are exemplified. In addition, surfactants and the like may also be added to these developing solutions. The development conditions can be appropriately selected, for example, in the range of temperature from 5 to 50°C and time from 10 to 600 seconds.</p><p>Subsequently, the pattern of the light-irradiating photoresist (upper layer) formed in this way is used as a protective film to remove the photoresist underlayer film (middle layer) of the present invention, followed by the patterned light-irradiating photoresist and the photoresist lower layer of the present invention The film formed by the film (middle layer) serves as a protective film to remove the organic underlayer film (lower layer). Finally, the patterned photoresist underlayer film (middle layer) and organic underlayer film (lower layer) of the present invention are used as protective films to process the semiconductor substrate.</p><p>In the above method, first, dry etching is used to remove the photoresist underlayer film (intermediate layer) of the present invention where the photoresist is removed by light irradiation, and expose the semiconductor substrate. The dry etching of the photoresist underlayer film of the present invention can use tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, boron trichloride and boron dichloride and other gases. In particular, the dry etching of the photoresist underlayer film of the present invention preferably uses a halogen-based gas. Dry etching using halogen-based gas is basically not easy to remove the light-irradiated photoresist formed by organic substances. Relatively, containing The photoresist underlayer film of the present invention with a large amount of silicon atoms can be quickly removed by halogen-based gas. Therefore, with the dry etching of the photoresist underlayer film, it is possible to suppress the reduction in the thickness of the photoresist film irradiated by light. Subsequently, as a result, a light-irradiated photoresist can be used as a thin film. The dry etching of the photoresist underlayer film can also be performed using a fluorine-based gas. Fluorine-based gas, for example, tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂)Wait.</p><p>The dry etching of the photoresist underlayer film of the present invention is preferably carried out by using halogen-based gases. Halogen-based gases, such as hydrogen bromide (HBr), chlorine (Cl), etc., can be combined with CF₄Or CHF₃Fluorine-based gas or O₂The mixture of oxygen-based gas and the like to obtain the etching selection ratio with the photoresist.</p><p>Subsequently, the patterned light is irradiated to the photoresist and the organic underlayer film formed of the photoresist underlayer film of the present invention as a protective film is removed. The organic underlayer film (lower layer) or the above-mentioned organic anti-reflection film is preferably removed by dry etching using an oxygen-based gas. Because the photoresist underlayer film of the present invention contains a large amount of silicon atoms, it is not easy to use oxygen-based gas to remove by dry etching.</p><p>Finally, the semiconductor substrate is processed. The processing of the semiconductor substrate is preferably performed by dry etching using fluorine-based gas.</p><p>Fluorine gas, for example, tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂)Wait.</p><p>In addition, the upper layer of the photoresist underlayer film of the present invention can be formed with an organic anti-reflection film before the photoresist is irradiated with light. The anti-reflection film composition used here is not particularly limited, and it can be made by photolithography so far. Among the customary contents in the process, any choice is used, and the customary methods, for example, use a spin coater or a strip coater for coating and sintering to form an anti-reflective film.</p><p>These multilayer manufacturing processes, for example, may include the step of forming an organic underlayer film on a semiconductor substrate, coating the photoresist underlayer film (thin film) forming composition of the present invention thereon, and form a photoresist underlayer film after sintering ( The step of the above-mentioned film), the step of coating the organic photoresist underlayer film forming composition on the aforementioned photoresist underlayer film to form an organic photoresist underlayer film, and the step of coating the photoresist composition on the aforementioned organic photoresist underlayer film, The step of forming a photoresist layer, the step of exposing the aforementioned photoresist film, the step of developing the photoresist film after exposure to obtain a photoresist pattern, and the step of etching the organic photoresist underlayer film through the photoresist pattern , The step of etching the photoresist underlayer film of the present invention (the above-mentioned film) through the patterned organic photoresist underlayer film, the step of etching the organic underlayer film by the patterned photoresist underlayer film, and the step of etching the organic underlayer film by the patterned photoresist underlayer film, and The patterned organic underlayer film is used to process the semiconductor substrate to produce a semiconductor device.</p><p>In addition, the substrate coated with the photoresist underlayer film forming composition of the present invention may be a substrate having an organic or inorganic anti-reflection film formed by CVD method or the like on the surface, and the substrate of the present invention may also be formed on the substrate. Underlayer film. The photoresist underlayer film formed by the photoresist underlayer film forming composition of the present invention has an absorption peak for the light depending on the wavelength of the light used in the photolithographic etching process. Subsequently, in this case, the photoresist underlayer film forming composition of the present invention has the function of an anti-reflection film that can prevent the effect of reflecting light from the substrate. In addition, the underlayer film of the present invention can be used as a layer that prevents the substrate from interacting with the photoresist when irradiated by light, and prevents the photoresist from being irradiated by light. The material used or the material generated when the photoresist is exposed to light is a layer with the function of adversely affecting the substrate, the layer with the function of preventing the material generated by the substrate from diffusing to the upper layer of the photoresist during heating and sintering, and the layer with the function of A barrier layer used to reduce the effect of contamination of the light-irradiated photoresist layer on the dielectric layer of the semiconductor substrate.</p><p>In addition, the photoresist underlayer film formed by the photoresist underlayer film forming composition of the present invention is suitable for a substrate with a vir hole formed in a dual damascene process. The use of buried material that does not create gaps in the holes. In addition, it can also be used as a flattening material for flattening the surface of the uneven semiconductor substrate.</p><p>Hereinafter, the case where the thin film forming composition of the present invention is used as an EUV photoresist underlayer film forming composition will be described.</p><p>In the present invention, the EUV photoresist coated on the upper layer of the EUV photoresist lower layer film can use either negative type or positive type. It can be used as, for example, a chemically amplified photoresist formed by a binder that has a base that is decomposed by an acid generator and an acid to change the rate of alkali dissolution, and has an alkali-soluble binder and an acid generator and acid. Decomposition, a chemically amplified photoresist formed by a low-molecular-weight compound that changes the alkali dissolution rate of the photoresist, has a base that is decomposed by an acid generator and an acid, and changes the alkali dissolution rate. A chemically amplified photoresist formed by decomposing low-molecular-weight compounds that change the alkali dissolution rate of the photoresist, and a non-chemically amplified photoresist formed by a binder that is decomposed by EUV to change the alkali dissolution rate. A non-chemically amplified photoresist, etc., formed by the bonding agent in the part where the alkali dissolution rate is changed by EUV.</p><p>A developer having a positive photoresist for a photoresist underlayer film formed using the EUV photoresist underlayer film forming composition of the present invention, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, methyl Inorganic bases such as sodium silicate and ammonia, primary amines such as ethylamine, n-propylamine, secondary amines such as diethylamine, di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine Alcoholamines such as dimethylethanolamine, triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, cyclic amines such as pyrrole, piperidine, and other bases Aqueous solution. In addition, surfactants such as alcohols such as isopropanol and non-ionic surfactants can be appropriately added to the aqueous solution of the alkalis and used. Among these, the preferred developer is a quaternary ammonium salt, and the most preferred are tetramethylammonium hydroxide and choline.</p><p>The present invention includes the step of forming the EUV photoresist underlayer film of the present invention on the substrate with the processing object film forming the transfer pattern, the step of forming the EUV photoresist film on the EUV photoresist underlayer film, and coating the EUV A method of manufacturing a semiconductor device in the step of exposing the semiconductor substrate of the photoresist film, and the step of developing after exposure to remove the photoresist film and the photoresist underlayer film.</p><p>Exposure was carried out according to EUV (wavelength 13.5nm).</p><p>In addition, for the EUV photoresist underlayer film, the above-mentioned photoresist underlayer film forming composition of the present invention can be used. The underlayer film of the EUV photoresist uses a kind of intermixing phenomenon that will not produce the phenomenon of intermixing with EUV photoresist, which can prevent inappropriate exposure light during EUV exposure, such as the reflection phenomenon of the above-mentioned UV or DUV caused by the substrate or interface Anti-reflective film under the EUV photoresist. The formed photoresist underlayer film of the present invention can effectively prevent reflection when it is used as the underlayer of EUV photoresist. As the EUV photoresist underlayer film is used, the process is The same method is used to irradiate the underlayer film for photoresist with light.</p><p>Hereinafter, the method of using the photoresist underlayer film forming composition of the present invention as an underlayer film of a photoresist for solvent development will be described.</p><p>Generally, the photoresist underlayer film forming composition of the present invention is coated on the above-mentioned substrate using a spin coater, a strip coater, etc. according to an appropriate coating method, and then the photoresist underlayer film is formed by sintering. Furthermore, before the photoresist underlayer film used in the present invention is coated, an organic underlayer film is formed on the substrate, and the above-mentioned thin film is formed thereon.</p><p>The light-irradiating photoresist formed on the thin film (photoresist underlayer film) of the present invention is not particularly limited as long as it can be exposed to light used for exposure such as ArF light. It can use either of a negative light irradiating photoresist and a positive light irradiating photoresist. After exposure, it can be used as long as light that can be developed by organic solvent irradiates the photoresist.</p><p>The above-mentioned conditions can be applied to the sintering conditions.</p><p>Secondly, on the photoresist underlayer film of the present invention, for example, the above-mentioned light-irradiating photoresist layer can be formed.</p><p>Similarly, in the present invention, it is also possible to use a photoresist for EUV lithography etching and a photoresist for electron lithography etching by changing the light irradiation photoresist to be used as the photoresist. EUV photoresist for photolithography and electron beam photoresist can be either negative or positive. The above-mentioned conditions can be used for the exposure conditions. After exposure, any photoresist that can be developed by organic solvents can be used.</p><p>Next, development is performed via a developer (organic solvent). In this way, for example, in the case of using positive light to irradiate the photoresist, the unexposed part of the light irradiating photoresist can be removed, and a pattern of the light irradiating photoresist can be formed.</p><p>Developers, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-heptanone, Propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene two Alcohol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate , Diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2 -Ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl Acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl 4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate , Ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetylacetate , Ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methyl Examples of oxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. In addition, the above-mentioned developer is more suitably used, such as butyl acetate, 2-heptanone, and the like.</p><p>In addition, surfactants and the like can be added to these developers. The development conditions can be appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.</p><p>Subsequently, the light-irradiating photoresist (upper layer) pattern formed in this way is used as a protective film to remove the photoresist underlayer film (middle layer) of the present invention, and then the patterned light is irradiated to the photoresist and the photoresist is used in the present invention. The film formed by the underlayer film (middle layer) is used as a protective film to remove the organic underlayer film (lower layer). Finally, the patterned photoresist underlayer film (intermediate layer) and organic underlayer film (lower layer) of the present invention are used as protective films to process the semiconductor substrate.</p><p>First, dry etching is used to remove the photoresist underlayer film (intermediate layer) of the present invention from which the light irradiated photoresist has been removed, to expose the semiconductor substrate. In the dry etching of the film of the present invention, tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, boron trichloride and boron dichloride and other gases. In particular, in the dry etching of the thin film of the present invention, it is preferable to use a halogen-based gas. Dry etching using halogen-based gas is basically not easy to remove the light-irradiating photoresist formed by organic substances. In contrast, the photoresist underlayer film of the present invention containing a large amount of silicon atoms can be quickly removed by halogen-based gas. Therefore, with the dry etching of the photoresist underlayer film of the present invention, the reduction in the thickness of the photoresist film irradiated by light can be suppressed. Therefore, as a result, the light-irradiating photoresist can be used as a thin film.</p><p>The dry etching of the film of the present invention is preferably to use a fluorine-based gas. The fluorine-based gas, for example, tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈),Complete Fluoropropane (C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂)Wait.</p><p>Subsequently, the film formed by irradiating the photoresist and the photoresist underlayer film of the present invention with patterned light serves as a protective film to remove the organic underlayer film. The organic underlayer film (lower layer) is preferably dry etching using an oxygen-based gas. Because the film of the present invention containing a large amount of silicon atoms is not easily removed by dry etching with oxygen-based gas.</p><p>Finally, the semiconductor substrate is processed. For the processing of semiconductor substrates, dry etching with fluorine-based gas is preferred.</p><p>Fluorine-based gas, for example, tetrafluoromethane (CF₄), perfluorocyclobutane (C₄F₈), perfluoropropane (C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂)Wait.</p><p>In addition, the thin film obtained from the photoresist underlayer film forming composition of the present invention can be used as a reverse material as long as a solvent that does not dissolve the photoresist is selected. In the method of using the reversal material, first, the photoresist underlayer film forming composition of the present invention is coated on the photoresist pattern formed on the substrate, and dried to form a thin film. The formed film is then etched back to expose the photoresist pattern surface, and dry etching is performed using a gas (for example, oxygen-based gas) that can selectively remove the photoresist, leaving only the thin film layer. Reverse the pattern.</p>

[Example]

(Production of methyl tungstic acid aqueous solution)

Make methyl ammonium tungstate (manufactured by Japan Inorganic Chemical Industry, WO₃(90.8% by mass converted) 20.0 g was dissolved in 80.1 g of ion-exchanged water to prepare an aqueous solution of methyl ammonium tungstate. 20.0 g of cation exchange resin (AMBERLIST 15JWET manufactured by Organic Company) was added, stirred at room temperature for 4 hours, and filtered to obtain an aqueous solution of methyl tungstic acid. The pH of the resulting solution was 0.54. The solid residue at 140°C was 17.0%.

(Synthesis example 1)

Add 18.94g (30mol%) of methyltriethoxysilane, 51.62g (70mol%) of tetraethoxysilane, and 105.84g of acetone into a 300ml flask. The mixed solution is stirred with a magnetic stirrer. , Drop 23.60 g of 0.01 mol/l hydrochloric acid into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 142.00 g of propylene glycol monomethyl ether was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone, which were by-products of the reaction, were distilled off under reduced pressure to obtain a concentrated hydrolysis condensate (polymer) of propylene glycol monomethyl ether. Methyl ether solution. The solution was diluted with propylene glycol monomethyl ether and adjusted to a solid residue of 30.0% by weight at 140°C. The obtained polymer corresponds to formula (5-1).

(Synthesis example 2)

Combine 3-(triethoxysilylpropyl) diallyl isocyanurate 18.99g (15mol%), tetraethoxysilane 44.65g (70mol%) methyltriethoxysilane 8.19 g(15mol%), 71.83g of acetone, add 300ml In the flask, the mixed solution was stirred with an electromagnetic stirrer, and 20.41 g of 0.01 mol/l hydrochloric acid was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 142.00 g of propylene glycol monomethyl ether was added to the reaction solution, and ethanol, water, hydrochloric acid, and acetone, which were by-products of the reaction, were distilled off under reduced pressure to obtain a concentrated hydrolysis condensate (polymer) of propylene glycol monomethyl ether. Methyl ether solution. The solution was diluted with propylene glycol monomethyl ether and adjusted to a solid residue of 30.0% by weight at 140°C. The obtained polymer corresponds to formula (5-2).

(Synthesis example 3)

Combine 9.63g (14mol%) of phenyltrimethoxysilane, 9.28g (15mol%) of methyltriethoxysilane, 50.59g (70mol%) of tetraethoxysilane, N-(3-(triethoxy) Silyl) propyl) phenamidine 1.25g (1mol%) and acetone 106.12g were added to a 300ml flask, the mixed solution was stirred with an electromagnetic stirrer, and 23.13g of 0.01mol/l hydrochloric acid was dropped into the mixed solution middle. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 142.00 g of propylene glycol monomethyl ether was added to the reaction solution, and methanol, ethanol, water, hydrochloric acid, and acetone, which were by-products of the reaction, were distilled off under reduced pressure to obtain a concentrated hydrolysis condensate (polymer) Propylene glycol monomethyl ether solution. The solution was diluted with propylene glycol monomethyl ether and adjusted to a solid residue of 30.0% by weight at 140°C. The resulting polymer corresponds to formula (5-8).

(Synthesis example 4)

Add 4.48g of methyltriethoxysilane, 15.73g of tetraethoxysilane, and 76.31g of methanol into a 300ml flask. The mixed solution was stirred with an electromagnetic stirrer, and the zirconium nitrate was added dropwise. Dihydrate (ZrO(NO₃)₂. 2H₂O) A solution obtained by dissolving 17.94 g in 76.31 g of methanol and 9.22 g of ultrapure water. After the addition, the flask was moved to an oil bath adjusted to 85°C, heated and refluxed, and reacted for 120 minutes. Subsequently, the reaction solution was cooled to room temperature, 200 g of propylene glycol monomethyl ether was added to the reaction solution, methanol, ethanol, and water as reaction by-products were distilled off under reduced pressure, and the solid residue at 140°C was adjusted to 15.0% by weight. The resulting polymer corresponds to formula (5-7).

(Manufacturing of photoresist underlayer film)

Mix methyl ammonium tungstate or methyl tungstic acid and the silicon-containing polymer, acid, hardening catalyst, additives, solvent, water, etc. obtained in the above synthesis example according to the ratio shown in Table 1, and filter with 0.1μm fluororesin As a result of filter filtration, a solution of the composition for forming a photoresist underlayer film was prepared. The addition ratio of the polymer in Table 1 is not the addition amount of the polymer solution, but the addition amount of the polymer itself.

In Table 1, maleic acid is abbreviated as MA and methanesulfonic acid is abbreviated as MeSO₃, Nitric acid is abbreviated as HNO₃, Benzyl triethyl ammonium chloride is referred to as BTEAC, triphenyl sulfonate trifluoromethane sulfonate is referred to as TPS105, maleic acid monotriphenyl sulfonate is referred to as TPSMA, and propylene glycol monomethyl ether is referred to as PGME. The water is ultrapure water. Each addition amount is expressed in parts by mass.

[Table 1]<tables><img file="TWI646153B_D0006.tif" he="2312" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1622" /></tables>

(Synthesis Example 5)

Add 25.81g (70mol%) of tetraethoxysilane, 9.47g (30mol%) of triethoxymethylsilane, and 52.92g of acetone into a 300ml flask and mix While the solution was stirred with an electromagnetic stirrer, 11.80 g of 0.01 mol/l hydrochloric acid was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and methanol, ethanol, acetone, water, and hydrochloric acid as reaction by-products were distilled off under reduced pressure. After concentration, the hydrolysis condensate (polymerization) was obtained. Material) Propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether is added to the solution, and the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether 20/80 is adjusted to a solid residue at 140° C., which is converted into 20 weight percent. The obtained polymer corresponds to formula (5-1), and the weight average molecular weight of GPC is Mw2000 in terms of polystyrene.

(Synthesis Example 6)

Add 25.59g (70mol%) of tetraethoxysilane, 6.26g (20mol%) of triethoxymethylsilane, 3.48g (10mol%) of phenyltrimethoxysilane, and 52.98g of acetone into a 300ml flask and mix While the solution was stirred with an electromagnetic stirrer, 11.69 g of 0.01 mol/l hydrochloric acid was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and methanol, ethanol, acetone, water, and hydrochloric acid as reaction by-products were distilled off under reduced pressure. After concentration, the hydrolysis condensate (polymerization) was obtained. Material) Propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether is added to the solution, and the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether 20/80 is adjusted to a solid residue at 140° C., which is converted into 20 weight percent. The obtained polymer is equivalent to formula (5-3), and the weight average molecular weight of GPC is After styrene conversion, it is Mw2000.

(Synthesis Example 7)

22.32g (70mol%) of tetraethoxysilane, 4.09g (15mol%) of triethoxymethylsilane, 3-(triethoxysilyl)propyl diallyl isocyanurate 9.49g (15mol%) and 53.88g of acetone were added to a 300ml flask, the mixed solution was stirred with an electromagnetic stirrer, and 10.20g of 0.01mol/l hydrochloric acid was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution was cooled to room temperature, 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and methanol, ethanol, acetone, water, and hydrochloric acid as reaction by-products were distilled off under reduced pressure . After concentration, the hydrolysis condensate (polymerization) was obtained. Material) Propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether is added to the solution, and the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether 20/80 is adjusted to a solid residue at 140° C. converted to 20 weight percent. The obtained polymer corresponds to formula (5-2), and the weight average molecular weight of GPC is Mw2000 in terms of polystyrene.

(Synthesis Example 8)

24.81g (70mol%) of tetraethoxysilane, 7.58g (25mol%) of triethoxymethylsilane, 3.08g of N-(3-(triethoxysilyl)propyl) phenylamidine (5mol%), 51.20g of acetone was added to a 300ml flask, the mixed solution was stirred with an electromagnetic stirrer, and 11.36g of 0.01mol/l hydrochloric acid was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution Cool to room temperature, add 68.00g of propylene glycol monomethyl ether acetate to the reaction solution, distill off the reaction by-products methanol, ethanol, acetone, water, and hydrochloric acid under reduced pressure, and concentrate to obtain the hydrolysis condensate (polymer) propylene glycol monomethyl Ether acetate solution. Propylene glycol monoethyl ether is added to the solution, and the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether 20/80 is adjusted to a solid residue at 140° C., which is converted into 20 weight percent. The obtained polymer corresponds to formula (5-4), and the weight average molecular weight of GPC is Mw2000 in terms of polystyrene.

(Synthesis Example 9)

Add 11.53g of silicotungstic acid, 3.48g of tetraethoxysilane, 4.47g of triethoxymethylsilane, and 77.95g of propylene glycol monomethyl ether into a 300ml flask. The mixed solution is stirred with an electromagnetic stirrer, and the ultrapure water 2.56 g was dropped into the mixed solution. After the addition, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution is cooled to room temperature, and ethanol and water, which are by-products of the reaction, are distilled off under reduced pressure to obtain a concentrated hydrolysis condensate (polymer) propylene glycol monomethyl ether solution. Propylene glycol monomethyl ether was added to this solution, and the solid residue adjusted to 140°C was converted to 20% by weight. The resulting polymer corresponds to formula (5-5).

(Synthesis example 10)

Put 11.53 g of silicotungstic acid, 11.98 g of tetra-n-butoxy hafnium, and 75.97 g of propylene glycol monomethyl ether into a 300 ml flask, and the mixed solution was stirred with an electromagnetic stirrer, and 5.04 g of concentrated nitric acid (70 wt%) was dropped into the flask. Mixed solution. Add to After that, the flask was moved to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 240 minutes. Subsequently, the reaction solution is cooled to room temperature, and ethanol and water, which are by-products of the reaction, are distilled off under reduced pressure to obtain a concentrated hydrolysis condensate (polymer) propylene glycol monomethyl ether solution. Propylene glycol monomethyl ether was added to this solution, and the solid residue adjusted to 140°C was converted to 20% by weight. The resulting polymer corresponds to formula (5-6).

(Production of Si-containing photoresist underlayer film)

The silicon-containing polymer, acid, hardening catalyst, sulfonate additive, solvent, and water obtained in the above synthesis example were mixed in the proportions shown in Table 1, and filtered with a 0.1μm fluororesin filter to obtain light. A solution of a composition for forming a barrier underlayer film. The addition ratio of the polymer in Table 2 is not the addition amount of the polymer solution, but represents the addition amount of the polymer itself.

Among the heteropoly acids in Table 2, (A) is silicotungstic acid, (B) is phosphotungstic acid, and (C) is phosphomolybdic acid.

In Table 2, maleic acid is abbreviated as MA, benzyltriethylammonium chloride is abbreviated as BTEAC, and N-(3-triethoxysilanpropyl)-4,5-dihydroimidazole is abbreviated as IMIDTEOS, triphenyl Chloride chloride is referred to as TPSC1, triphenylsilium maleate is referred to as TPSMA, triphenylsilium nitrate is referred to as TPSNO3, triphenylsilium trifluoroacetate is referred to as TPSTFA, triphenylsilanium camphorsulfonate is referred to as It is abbreviated as TPSCS, bisphenyl sulfide is abbreviated as BPS, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, propylene glycol monoethyl ether is abbreviated as PGEE, and propylene glycol monomethyl ether is abbreviated as PGME. The water is ultrapure water. Each addition amount is expressed in parts by mass.

<tables><img file="TWI646153B_D0007.tif" he="2768" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1649" /></tables>

Production of organic underlayer film forming composition

Under nitrogen, add carbazole (6.69g, 0.040mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28g, 0.040mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and Toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.), stirred and heated to 100°C. The dissolution begins to polymerize. After allowing to cool to 60°C after 24 hours, chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to dilute, and reprecipitation was performed using methanol (168 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered and dried at 80°C for 24 hours using a reduced pressure dryer to obtain 9.37 g of the target polymer (formula (6-1), hereinafter referred to as PCzFL).

<chemistry general="n"><img file="TWI646153B_D0008.tif" he="552" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1506" /></chemistry>

Of PCzFL¹The measurement results of H-NMR are shown below.

¹H-NMR(400MHz, DMSO-d₆): δ7.03-7.55(br, 12H), δ7.61-8.10(br, 4H), δ11.18(br, 1H) The weight average molecular weight Mw of polystyrene conversion obtained by GPC measurement of PCzFL is 2800, The polydispersity Mw/Mn is 1.77.

In 20 g of the obtained resin, 3.0 g of tetramethoxymethyl acetylene carbamide (manufactured by Mitsui Technology Co., Ltd., trade name POWER-LINK 1174) as a crosslinking agent and 0.30 g of pyridinium p-toluenesulfonate as a catalyst are mixed , As an interface 0.06 g of Mega Fluor R-30 (manufactured by Dainippon Paint Chemical Co., Ltd., trade name), which is a sex agent, was dissolved in 88 g of propylene glycol monomethyl ether acetate as a solution. Then, filter with a polyethylene microfilter with a pore size of 0.10μm, and then filter with a polyethylene microfilter with a pore size of 0.05μm to form an organic underlayer film for the lithographic etching process through a multilayer film.PhysicalSolution.

(Optical constant measurement)

Using a spin coater, the photoresist underlayer film forming compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 3 were respectively coated on the silicon wafer. Heat on a hot plate at 200°C for 1 minute to form a photoresist underlayer film (film thickness: 0.05 μm). Subsequently, these photoresist underlayer films were measured using a Spectroscopic Ellipsometer (manufactured by JA Woollam, VUV-VASEVU-302) to measure the refractive index (n value) and optical absorption coefficient (also known as k) at a wavelength of 193 nm. Value, attenuation coefficient).

(Measurement of dry etching speed)

The etcher and etching gas used for the measurement of the dry etching rate are those shown below.

ES401 (Japan SCIENTIFIC system): CF₄

RIE-10NR (manufactured by SAMCO): O₂

Using a spin coater, the solution of the photoresist underlayer film forming composition prepared in Examples 1 to 26 and Comparative Examples 1 to 3 was coated on the silicon wafer. On the hot plate, heat for 1 minute at the temperature listed in Table 3 and Table 4. Form a photoresist underlayer film (film thickness 0.08μm (measure CF₄Gas etching speed), 0.05μm (measure O₂The etching speed of the gas is used). In addition, the organic underlayer film was formed into a composition in the same manner using a spin coater, and a coating film (film thickness 0.20 μm) was formed on the silicon wafer. The etching gas is O₂The dry etching rate was measured by gas, and the dry etching rates of the photoresist underlayer films of Examples 1 to 26 and Comparative Examples 1 to 3 were compared.

Table 3 lists the refractive index n at a wavelength of 193nm, the optical absorption coefficient k at a wavelength of 193nm, Examples 1 to 11, and Comparative Examples 1 to 2 of the fluorine-based gas (CF₄Gas) and oxygen-based gas (O₂Gas) etching rate (etching rate: nm/min).

<tables><img file="TWI646153B_D0009.tif" he="1476" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1590" /></tables>

Table 4 shows the refractive index n at 193nm wavelength and the optical absorption coefficient k at 193nm wavelength. The fluorine-based gas (CF₄Gas) etching rate (etching Speed: nm/min), oxygen gas (O₂The gas resistance is the etching rate ratio of (photoresist underlayer film)/(organic underlayer film).

<tables><img file="TWI646153B_D0010.tif" he="1569" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1493" /></tables>

(Patterning evaluation 1)

The above-obtained organic underlayer film (layer A) formation composition was coated on a silicon wafer, and baked on a hot plate at 400° C. for 60 seconds to obtain an organic underlayer film (layer A). On it, the photoresist underlayer film (layer B) obtained in Examples 1 to 26 and Comparative Examples 1 to 3 was respectively coated to form the composition, and the composition was calcined on a hot plate at the temperature shown in Table 5 and Table 6 for 60 seconds Zhong, the photoresist underlayer film (layer B) was prepared.

On top of it, use a spin coater to irradiate the commercially available light to the photoresist solution (JSR Co., Ltd., trade name AR2772) was coated on it, and baked on a hot plate at 110°C for 60 seconds to form a light-irradiated photoresist film (layer C) with a film thickness of 120 nm. The patterning of the photoresist was performed using Nikon's ArF exposure machine S-307E (wavelength 193nm, NA, σ: 0.85, 0.93/0.85 (Dipole) dipping solution: water). The target is to make the line width of the photoresist irradiated by the developed light and the width between the lines to 0.062μm, that is, exposure is performed by setting a mask that forms lines and spaces (dense lines).

Subsequently, it was calcined on a hot plate at 110° C. for 60 seconds, and after cooling, it was developed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution (developer) in a single paddle stirring type step for 60 seconds. In the photoresist pattern skirt shape after lithography etching, the line with rectangular shape is called "straight", the line with thick bottom is called "foot", the line with thin bottom is called "undercut", and the photoresist section Those with a wavy shape are called "standing waves".

After the photoresist pattern is formed, the shape of the photoresist skirt is good if the circuit is rectangular, and the shape of the photoresist skirt is bad if the shape of the photoresist skirt is deteriorated.

[table 5]<tables><img file="TWI646153B_D0011.tif" he="1241" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1518" /></tables>

<tables><img file="TWI646153B_D0012.tif" he="1594" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1526" /></tables>

(Evaluation of photoresist pattern formation 2)

The above-obtained organic underlayer film (layer A) forming composition was coated on a silicon wafer, and baked on a hot plate at 400° C. for 60 seconds to obtain an organic underlayer film (layer A). On it, the photoresist underlayer film (layer B) obtained in Examples 1 to 26 and Comparative Examples 1 to 2 was coated to form the composition, and baked on a hot plate at the temperature shown in Table 7 and Table 8 for 60 seconds. Obtain the photoresist underlayer film (layer B).

On it, a commercially available light-irradiation photoresist solution (manufactured by Fuji Film Co., Ltd., trade name FAiRS-9521NT05) was applied separately on it using a spin coater, and heated on a hot plate at 100°C for 1 minute to form a film with a thickness of 85 nm. Light irradiates the photoresist film (layer C).

Using (stock) Nikon NSR-S307E scanner (wavelength 193nm, NA, σ: 0.85, 0.93/0.85), the line width of the photoresist is irradiated with the developed light and the width between the lines is 0.060μm, that is, 0.060μm The dense line of line and space (L/S)=1/1 is exposed through the set mask. Subsequently, it was baked on a hot plate at 100°C for 60 seconds, and after cooling, it was developed with butyl acetate (solvent developer) for 60 seconds to form a negative pattern on the photoresist underlayer film (layer B). The resulting light-irradiated photoresist pattern is one that has no large-scale pattern peeling or undercutting, and hypertrophy (footing) at the bottom of the circuit, and is evaluated as good ("straight").

[Table 7]<tables><img file="TWI646153B_D0013.tif" he="1267" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1520" /></tables>

<tables><img file="TWI646153B_D0014.tif" he="1589" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="1507" /></tables>

[Industrial Utilization]

The thin film forming composition of the present invention can be used in photoresist underlayer film forming compositions such as ArF and KrF light irradiation photoresist, photoresist underlayer film forming compositions such as EUV photoresist, and photoresist underlayer film forming compositions such as electron beam photoresist. , Reverse (reverse) material to form a composition, etc.