TW201100968A - Resist underlayer film forming composition containing polymer having acetal structure on side group and method for forming resist pattern - Google Patents

Abstract

Disclosed is a composition for forming a resist underlayer film, which contains a polymer having an acetal structure in a side chain thereof. Also disclosed is a method for forming a resist pattern. Specifically disclosed is a composition for forming a resist underlayer film, which comprises a component (A), a component (B) and a solvent. The component (A): a polymer having a constituent unit represented by formula (1) and having a weight average molecular weight of 1,000 to 200,000. The component (B): a crosslinkable compound. [In the formula, R1 represents a hydrogen atom or a methyl group; R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R3 represents a hydrogen atom or a methyl group; P represents a bivalent organic group; and Q represents an unsubstituted naphthalene ring (a naphthyl group) or anthracene ring (an anthracenyl group), or a naphthalene ring (a naphthyl group) or anthracene ring (an anthracenyl group) having at least one substituent selected from a group consisting of a hydroxy group, a carboxyl group, a halogen atom, a sulfonyl group, an amino group, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atom and an aryl group.]

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a photoresist pattern using a photoresist underlayer film formed of a photoresist underlayer film and the composition. More specifically, there is a method of forming a photoresist pattern using a photoresist underlayer film forming composition and a photoresist underlayer film formed by the composition when an alkali developing solution is used. ❸ [Prior Art] In the lithography step, there is a problem that the influence of the standing wave reflected by the exposure light from the substrate or the difference in the substrate length causes the exposure light to be diffused, resulting in a decrease in the accuracy of the resist pattern. Therefore, in order to improve the pattern accuracy after exposure and development, a method of providing an anti-reflective coating (Bottom Anti-Reflective Coating) between the photoresist and the substrate has been widely studied. These antireflection films are formed by using a thermally crosslinkable composition in order to prevent mixing with the photoresist applied thereto. As a result, the formed antireflection film becomes insoluble in the alkaline developer used for photoresist development. Therefore, it is necessary to remove the antireflection film by dry etching before processing the semiconductor substrate (for example, refer to Patent Document 1). However, the antireflection film is removed by dry etching while the photoresist is also dry etched. Therefore, it has become difficult to ensure the thickness of the photoresist film required for substrate processing. Especially for the purpose of improving the resolution, the use of thin film photoresist becomes a major problem. Therefore, in order to solve this problem, a method of designing an antireflection film DBARC (Developable Bottom Anti-Reflective Coating) which exposes an exposed portion together with a photoresist is proposed. 201100968 The antireflection film used in this method must be a film which is soluble in the alkaline developing solution used for photoresist development and which is developed and removed simultaneously with the photoresist. Next, various antireflection films which can be simultaneously removed by photoresist development are currently discussed (refer to Patent Documents 2 to 6). Such an antireflection film is typically composed of a polymer having a hydroxyl group and/or a carboxyl group in a side chain, a vinyl ether crosslinking agent, and a photoacid generator. Next, in order to further enhance the antireflection function of such an antireflection film, a chromophore having light absorption at an exposure wavelength of KrF or the like is incorporated into a film-forming polymer, and it is proposed to contain, for example, such a chromophore. a polymer composed of at least one repeating unit, a repeating unit having at least one of a hydroxyl group and/or a carboxyl group, a crosslinking agent having a terminal vinyl ether group, a photoacid generator and/or an acid and/or Or an antireflection film forming composition of a thermal acid generator (refer to Patent Document 7). The polymer of the antireflection film forming composition reacts with a crosslinking agent having a vinyl ether group to carry out crosslinking by acetal bonding. Thereafter, the machine is converted into a photoacid generator contained in the obtained antireflection film and photoresist, and an acid is generated during exposure, and the acetal bond is detached due to the acid to be decrosslinked, and becomes soluble in the alkali developer. . However, this anti-reflection film solution is such that the alkali solubility of the polymer after decrosslinking is lowered, which tends to cause residue. The reason why the polymer is hardly soluble in the alkali developing solution is mostly due to the hydrophobicity of the chromophore contained in the polymer. [Patent Document 1] [Patent Document 1] US Pat. No. 6,156,479 [Patent Document 2] JP-A-2004-54286 (Patent Document 3) JP-A-2005-70154, JP-A-201100968 [Patent Document 4] International Publication No. 05/093 5 1 3 [Patent Document 5] International Publication No. 05/111719 [Patent Document 6] International Publication No. 5/1 1 1 724 [Patent Document 7] Special Table 2008-501985 [Problem to be Solved by the Invention] The present invention has been made in view of the above-described reasons, and an object of the invention is to provide an acetal represented by the following formula (I) or formula (II) by a highly hydrophobic chromophore. The bond is contained in the polymer to solve. Provided by the acid generated at the time of exposure, not only the crosslinked structure of the acetal of the crosslinking agent but also the bond represented by the following formula (I) or formula (II) is cleaved, and as a result, the chromophore group leaves the polymer, so polymerization is carried out. The alkali solubility of the material itself is improved, and even if the alkaline developing solution is used for development of the photoresist underlayer film, the photoresist underlayer film forming composition and the photoresist pattern of the photoresist underlayer film formed by the composition can be reduced. Forming method. Further, the present invention provides a photoresist-forming underlayer film forming composition for a short-wavelength light, such as an ArF excimer laser (wavelength 193 nm) and a KrF excimer laser (wavelength 248 nm). . Further, the present invention provides effective formation of reflected light from a semiconductor substrate and does not generate light from a photoresist film when micro-processing for forming an ArF excimer laser and a KrF excimer laser is used for the lithography step. The photoresist underlayer film for the mixed photoresist underlayer film forms a composition. 201100968 【化1】

(wherein R 2 is a hydrogen atom or an alkyl group having 1 or 3 carbon atoms, and r 3 is a hydrogen atom or a methyl group). [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have found that the chromophore introduced into the light absorbing portion at the side chain of the polymer by the bonding represented by the above formula (I) or (II) is found. (chromophore), in order to improve the alkali solubility of the polymer, the present invention has been completed. That is, the first aspect of the present invention is a photoresist base film forming composition containing the component (A), the component (B), and a solvent: (A) component: the weight of the structural unit represented by the following formula (1) Polymer with an average molecular weight of 1,000 or 200,000 (B) Component: crosslinkable compound 201100968 [Chemical 2]

0) Ο {wherein, R! is a hydrogen atom or a methyl group, R2 is a hydrogen atom or an alkyl group having 1 or 3 carbon atoms, R3 is a hydrogen atom or a methyl group, P is a divalent organic group, and Q is an unsubstituted Naphthalene ring (naphthyl) or anthracene (fluorenyl) or having an alkyl or aryl group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen atom, a sulfonyl group, an amine group, a cyano group, a nitro group, and having 1 to 10 carbon atoms A naphthalene ring (naphthyl) or an anthracene ring (fluorenyl) of at least one substituent in the group. The second aspect of the present invention is a photoresist base film forming composition containing Q (A') component, (B) component, and solvent: (A,) component: having the weight of the structural unit represented by the following formula (6) Polymer (B) having an average molecular weight of 1,0 〇〇 or even 200,0 0: crosslinkable compound 201100968 [Chemical 3]

Re A (6) person

I p { wherein R! is a hydrogen atom or a methyl group, R6 is a benzene ring or a direct bond, and P is a divalent organic group, and Q is an unsubstituted naphthalene ring (naphthyl group) or an anthracene ring (fluorenyl group). Or a naphthalene ring having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen atom, a sulfonyl group, an amine group, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms or an aryl group (naphthalene) Base) or 蒽 ring (蒽基)}. A third aspect of the present invention is a step of forming a photoresist underlayer film by coating and baking a photoresist underlayer film forming composition of the present invention on a semiconductor substrate, and forming a photoresist film on the photoresist underlayer film. a step of exposing the photoresist underlayer film and the semiconductor substrate covered by the photoresist film, and a step of developing the photoresist film and the photoresist underlayer film after exposing to a photoresist pattern for semiconductor device fabrication The method of formation. [Effect of the Invention] The composition of the photoresist base film of the present invention is such that a chromophore (naphthalene ring or an anthracene chromophore) which absorbs light at an exposure wavelength of KrF or the like is transmitted through the following formula (I) or formula (II). The bond is represented by the bond to the polymer backbone. Therefore, 'exposure time' generates an acid of -10-201100968 by the photo-acid generator contained in the upper layer photoresist and the photoresist underlayer film, not only the acetal cross-linking structure of the crosslinking agent of the photoresist underlayer film, and the above formula The bond represented by (I) or formula (II) is also cut off. Then, the light absorbing portion formed by the above chromophore is also deprotected, and the alkali solubility of the polymer itself is improved. Therefore, the alkali solubility of the photoresist base film formed by baking the composition is improved, and even if an alkali developer is used to develop the photoresist underlayer film, the generation of residue can be remarkably reduced. Further, the photoresist base film of the present invention forms a composition which can form, for example, an ArF excimer laser (wavelength 193 ηπι) and a KrF excimer laser (wavelength 248 nm) by introduction of the above chromophore. A short-wavelength light has a strongly absorbing photoresist underlayer film. Further, the photoresist base film formed by forming the composition of the photoresist base film of the present invention can effectively absorb the semiconductor from the semiconductor by using the ArF excimer laser or the KrF excimer laser to irradiate the light in the microfabrication step. The substrate reflects light and does not mix with the photoresist film. Further, when the photoresist base film is formed using the photoresist base film of the present invention, the polymer of the component (A) or the polymer of the component (A) and the carboxyl compound of the component (D) have a carboxyl group. Or a group in the case of a hydroxyl group, and a group in which the photoacid generator of the component (C) has a carboxyl group or a hydroxyl group, and a crosslinkable compound of the component (B) is thermally crosslinked to form a plurality of shrinkage in the photoresist underlayer film. In the aldehyde bond, after the exposure and development, the bonding is often cut, and the alkali developability is good, so that a fine pattern can be produced and the resolution can be improved. -11 - 201100968

(I) Ο^Ό Person (Π) (wherein R2 is a hydrogen atom or a group of 1 or 3 carbon atoms, and r3 is a hydrogen atom or a methyl group). BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component will be described in detail. The total solid content of the solvent for removing the composition of the photoresist base film of the present invention is 0.1 to 70% by mass, preferably 1 to 60% by mass. <Component (A)> The polymer of the component (A) is a polymer having a weight average molecular weight of 1, unit 〇〇〇 or 200,000, which has a unit structure represented by the following formula (1). 【化5】

-12- 201100968 {wherein, Ri is a hydrogen atom or a methyl group, R2 is a hydrogen atom or an alkyl group having 1 or 3 carbon atoms, R3 is a hydrogen atom or methyl 'P is a divalent organic group' Q is unsubstituted Naphthalene ring (naphthyl) or anthracene (fluorenyl) or having an alkyl or aryl group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen atom, a sulfonyl group, an amine group, a cyano 'nitro group, and a carbon number of 1 to 10 A naphthalene ring (naphthyl) or an anthracene ring (fluorenyl) of at least one substituent in the group. As the polymer of the component (A), for example, a polymer having a structure represented by the following formula (a) to formula (e) can be used.

(d) (e) -13- 201100968 <(A') component> The polymer of the component (A) is a polymer having a weight average molecular weight of 1,000 to 200,000 as a structural unit represented by the following formula (6).

Wherein R is a hydrogen atom or a methyl group, R6 is a benzene ring or a direct bond ' and P is a divalent organic group' Q is an unsubstituted naphthalene ring (naphthyl group) or an anthracene ring (fluorenyl group) or has Naphthalene ring (naphthalene) selected from the group consisting of a hydroxyl group, a carboxyl group, a chelating group, a sulfonyl group, an amine group, a cyano group, a nitro group, an alkyl group having 1 or 1 Å, or an aryl group The above-mentioned divalent organic group p' is a group represented by the following formula (2) or formula (3), or a carbon atom, in the above formula (1) or (6). Number 1 or even 10

201100968 {In the formulas (2) and (3), m and η are each independently an integer of 1 to 10} Further, the polymer of the above (Α) component is a structural unit other than the structural unit represented by the above formula (1) Further, it may have a structural unit represented by the following formula (4).

(wherein R4 is a hydrogen atom or a methyl group). Further, the polymer of the above (Α) component may have a structure other than the structural unit represented by the above formula, and may have a stomach pq —· a single enthalpy. 〇 【化1 0】 / R7\

Wherein R7 is a hydrogen atom or a methyl group, and j is 0 or 1. · When J is 0, a phenyl group having a hydroxyl group as a substituent is directly bonded to the main chain. In addition, when /b, j is , A is -C(=0)-NH-group or -〇(=0)-0-base}. Further, the polymer of the component (A) is substituted with the structural unit other than the structural unit represented by the above formula (1) as the structural unit represented by the above formula (4), or the structure represented by the above formula (4) Outside the unit, a structural unit represented by the following formula (5) can be used. [1 1

(5) (wherein R5 is a hydrogen atom or a methyl group, X is an alkyl group having 1 to 10 carbon atoms or a phenyl group, and k is a number represented by X, and k is 0 or 1. However, When k is 0, the carboxyl group is directly bonded to the main chain). The structural unit other than the structural unit represented by the above formula (6) may be a structural unit represented by the above formula (7) or a structural unit represented by the above formula (7).倂 has the structural unit represented by the above formula (5). In the above alkylene group and in the present specification, when the number of carbon atoms of the alkylene group below is 3 or more, the alkylene group is not limited to a linear chain or a branched form. Here, when the polymer of the component (A) also has a structural unit represented by the above formula (4) or (5), the molar ratio of the above formula (1) to the above formula (4) or the above formula (5) 1: 1 to 10000, preferably 100: 10 or 1000 〇 Similarly, when the polymer of the above (A,) component also has the structural unit represented by the above formula (5) or formula-16-201100968 (7) The molar ratio of the above formula (6) to the above formula (5) or the above formula (7) is from 100:1 to 10,000, preferably from 100:10 to 1000 °. The photoresist base film of the present invention forms a composition ( The content of the polymer of the component A) relative to the solid content of the photoresist underlayer film forming composition is 1% by mass or more, for example, 30% to 99% by mass, or 49% to 90% by mass, preferably 5<9> or even 80% by mass. Further, the content of the polymer of the (A,) component of the composition of the photoresist film of the present invention in the solid content of the composition of the photoresist underlayer film is from 1 to 99% by mass, preferably 10 Even 95% by mass, more preferably 50 or 90% by mass. Since the ratio is too small and too large, it becomes difficult to obtain solvent resistance. The weight average molecular weight of the polymer of the above component (A) is, for example, 1,000 to 200,000, preferably 3,000 or 20,000. Further, the weight average molecular weight of the polymer of the above (A') component is preferably from 1, 乃 to 200,000, more preferably from 3,000 to 100,000. When the weight average molecular weight of the polymer is less than 30 〇 ,, the solvent resistance may be insufficient, and if the weight average molecular weight is too large, there is a problem that the resolution is problematic. Further, the weight average molecular weight is obtained by colloidal permeation chromatography (GPC) using polystyrene as a standard sample. &lt;(B) component&gt; The crosslinkable compound as the component (B) is, for example, a compound having at least two 201100968 vinyl ether groups. Next, the compound having at least two vinyl ether groups means a compound having 2 to 20, preferably 3 to 10, more preferably 3 to 6 vinyl ether groups. The crosslinkable compound 'for example, bis(4-(ethylideneoxymethyl)cyclohexylmethyl)glutarate, tris(ethylene glycol) divinyl ether, divinyl adipate, one Ethylene glycol divinyl ether, tris(4-vinyloxy)butyl terephthalic acid, bis(4-(ethylideneoxy)butyl)terephthalate, double (4_(ethyl anaerobic) Isobutyl)isophthalate, cyclohexanedimethanoldivinyl acid, H-butanol-ethylene-based acid, mono-glycol diethylene ether, dipropylene glycol divinyl ether, three Hydroxymethylpropane trivinyl ether and pentaerythritol tetraethyl sulphate. These compounds may be used alone or in combination of two or more. Further, the crosslinkable compound (B) is preferably a compound represented by the following formula (8) or formula (9). [Chemical 1 Ql one

r (where q is an integer from 1 to ίο). -18- (9) (9)201100968 [Chem. 1 3]

(wherein r is an integer from 1 to 10). The content of the crosslinkable compound (b) used for the polymer of the component (A) is 0.01% to 60% by mass based on the content of the solid content of the photoresist underlayer film forming composition of the present invention, for example, 0.1 or even 50 mass. /. , or 0.1 or even 40% by mass. Further, the content of the crosslinkable compound (B) used for the polymer of the above (A') component is 1 to 70% by mass based on the content of the solid content of the composition for forming the photoresist underlayer film. It is preferably 3 or 60% by mass, more preferably 5 or 50% by mass. When the ratio is too small or too large, it becomes difficult to obtain solvent resistance &lt;(C) component&gt; The photoresist base film forming composition of the present invention may contain a photoacid generator as the component (C). The photoacid generator may, for example, be a compound which generates an acid by irradiation with light used for exposure, for example, a diazomethane compound, a key salt compound, a sulfonimide compound, a nitrobenzyl compound, benzoin p-toluenesulfon-19-201100968 An acid salt compound, a halogen-containing triazine compound, a cyano group-containing sulfonate compound, and the like. Among these, a key salt compound is preferred. The key salt compound is exemplified by diphenyl sulfonium hexafluorophosphate, diphenyl iodine triflate, diphenyl iodine hexafluoro-n-butane sulfonate, diphenyl.捵Key perfluoro-η-octane sulfonate, diphenyl iodonium camphorsulfonate, bis(4-tert-butylphenyl) iodine camphorsulfonate and bis(4 tert-butylphenyl) a key salt compound such as iron iodide difluoromethane nitrate or triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-η-butanesulfonate, triphenyl camphorsulfonate An anthracene salt compound such as diphenyl mirror trifluoromethanecarboxylate or triphenylsulfonium p-toluenesulfonate. The sulfonimide compound may, for example, be Ν-(trifluoromethanesulfonyloxy) succinimide, Ν-(nonafluoro-η-butanesulfonyloxy) succinimide, Ν-( camphor Sulfohydryloxy) succinimide and hydrazine-(trifluoromethanesulfonyloxy)naphthylimine. The content of the photo-acid generator (C) used for the polymer of the above (Α) component is 0.01% to 15% by mass based on the content of the solid content of the photoresist underlayer film forming composition of the present invention, or 0.1 to 10% by mass. When the ratio of use of the photoacid generator (C) is less than 0.01% by mass, the ratio of the amount of generated acid is small, and as a result, the solubility of the exposed portion in the alkaline developing solution is lowered, and the residue may be present after the development. When it exceeds 15 mass%, the storage stability of the photoresist underlayer film formation composition is lowered, and as a result, the shape of the photoresist is affected. Further, the content of the photo-acid generator (C) used for the polymer of the above (Α') component is relative to the content of the solid--20-201100968 component of the composition of the photoresist base film of the present invention. It is 0 or 10% by mass, preferably 〇% or even 5% by mass. When the ratio is 1 〇 mass% or more, the storage stability of the photoresist underlayer film forming composition is lowered, and the shape of the photoresist is affected. &lt;Component (D)&gt; The photoresist base film forming composition of the present invention may contain a basic compound as the component (D). By adding a basic compound, the sensitivity of the photoresist undercoat film can be adjusted. Therefore, the reaction of the basic compound with the acid generated by the photoacid generator during exposure can lower the sensitivity of the photoresist underlayer film. Further, it is possible to suppress the diffusion of the acid generated by the photoacid generator in the photoresist underlayer film of the exposed portion to the photoresist underlayer film of the unexposed portion. The above basic compounds are, for example, amines, ammonium hydroxides and the like. The above amines are not particularly limited, and examples thereof include triethanolamine, tributylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine oxime, and tri-n- Tertiary amines such as butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane Or an aromatic amine such as pyridine or 4-dimethylaminopyridine. Further, for example, a second-stage amine such as a first-grade amine such as benzylamine or η-butylamine, diethylamine or di-η-butylamine may be mentioned. The above-mentioned amines can be infiltrated into the polymer of the (Α) component or the polymer of the (Α') component, in addition to inhibiting the acid generated by the above photoacid generator from diffusing to the photoresist film of the unexposed portion. a crosslinked polymer formed by thermal crosslinking of the component crosslinkable compound, and then an acid produced by the photoacid generation of the component (C) in the exposed portion is crosslinked and cleaved to form a hydroxyl group. It exhibits solubility in an alkali developer. Therefore, the basic compound of the component (D) preferably has a hydroxyl group, and triethanolamine or tributylamineamine is particularly preferred. The above basic compounds may be used singly or in combination of two or more kinds. The content of the basic compound (D) for use in the polymer of the component (A) is 0.001 to 5 parts by mass, for example, 0.01 to 1 part by mass, per 100 parts by mass of the polymer of the component (A). , or 0.1 or 0.5 parts by mass. Further, the content of the basic compound (D) used for the polymer of the above (A') component is in the form of a solid content of the composition of the photoresist base film of the present invention, which is 〇 or even 1 〇 mass. %, preferably 〇 or even 5 mass%, more preferably 0 or even 1 mass%. Since this ratio is larger than the above, the sensitivity is lowered. Further, the photoresist underlayer film forming composition of the present invention may further contain an interface active agent. The surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene decyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene oleyl ether, etc. Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block homopolymers, sorbitan Monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Esters and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy-22- 201100968 ethylene sorbitan Nonionic interface of polyoxyethylene sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate Active agent, EFTOPEF301, EF303, EF 3 5 2 (Mit sub i shi Materials Electronic Transformation Co., Ltd. (old (share)] 6111 (: 〇) system), 1 \ ^ 0 people? Eight 〇 ugly? 171, 173, R30 (DIC company (old Japan ink chemical industry (share))), FluoradFC430, FC431 ( Sumitomo 3M (share) system, AsahiGuard AG7 1 0 〇, Surflon S-3 82, SCI 01, SC102, SC103, SC104, SC 105, SC 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organic helium oxygen An alkane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. These surfactants may be used singly or in combination of two or more kinds. The content of the surfactant used in the polymer of the above (Α) component is In the total composition of the photoresist underlayer film forming composition of the invention, it is usually 0.2% by mass or less, preferably 0.1% by mass or less. Further, the surfactant of the polymer used for the above-mentioned (Α,) component is contained in the composition. The content 'in the solid content of the photoresist underlayer film forming composition of the present invention' is 3% by mass or less, preferably 丨% by mass or less, more preferably 5% by mass or less. Further 'The present invention The photoresist underlayer film composition may contain rheology according to other needs The adjusting agent, the auxiliary agent, etc. The photoresist underlayer film forming composition of the present invention can be prepared by dissolving the above components in a suitable solvent to obtain a uniform solution. The solvent can be used, for example, ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl-23-201100968 ether, diethylene glycol monoethyl ether, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxypropionic acid Ester, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3·-methylbutanoate, methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate Ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone. Further, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be used. These solvents may be used singly or in combination of two or more kinds. It is preferred to use a filter (form solution) for forming a photo-resistance underlayer film to be prepared by filtering using a filter having a pore diameter of, for example, about 0.2 μm. The composition of the photoresist base film formed in this manner is excellent in storage stability over a long period of time. Hereinafter, the use of the photoresist underlayer film forming composition of the present invention will be described. a substrate such as a semiconductor substrate coated with a tantalum oxide film, a semiconductor substrate coated with a tantalum nitride film or a tantalum nitride film, a tantalum nitride substrate, a quartz substrate, or a glass substrate (including none) The alkali-cured glass, the low-alkali glass, the crystallized glass), the glass substrate on which the ruthenium film is formed, etc., the composition of the photoresist base film of the present invention is applied by a suitable coating method such as a spin coater, and then, Baking is performed using a heating means such as a hot plate to form a photoresist underlayer film. The baking conditions can be suitably selected from a baking temperature of 80 ° C or even 250 ° C, a baking time of -24 to 201100968, 0.3 minutes or even 60 minutes. Preferably, the baking temperature is 130 ° C or even 25 ° C, and the baking time is 0.5 minutes or even 5 minutes. When the baking temperature is lower than the above range, the crosslinking of the photoresist underlayer film becomes insufficient, and the photoresist underlayer film and the photoresist are mixed. Further, when the baking temperature is too high, cross-linking of the photoresist underlayer film is cut off, and the photoresist underlayer film and the photoresist are mixed. Further, the film thickness of the photoresist base film of the present invention is Ο.ΟΟΙμπι or even 〇3·0μπι, for example, Ο.ΟΙμηι or even 1·0μιη, or 0.03μιη or even 0·5μπι. The photoresist base film formed by the composition of the photoresist base film of the present invention is subjected to a baking condition at the time of formation, and the vinyl ether compound is crosslinked to form a strong film. Therefore, the photoresist underlayer film formed by the photoresist underlayer film forming composition of the present invention does not mix with the photoresist. Next, the photoresist solution coated on the film is a general organic solvent used, such as ethylene glycol monomethyl ether, ethylene cellosolve acetate, diethylene glycol monoethyl ether, propylene glycol, Propylene glycol monomethyl ether, propylene glycol monomethyl decyl ether acetate, propylene glycol propyl ether acetate, toluene, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl pyruvate, ethyl lactate and butyl lactate. A photoresist film is then formed on the photoresist underlayer film. The formation of the photoresist film can be carried out by a general method, that is, coating and baking of the photoresist solution on the photoresist underlayer film. The photoresist formed on the photoresist underlayer film obtained by forming the composition of the photoresist underlayer film of the present invention is not particularly limited as long as it is photosensitive to the exposure light and is expressed as -25-201100968. The photoresist includes, for example, a positive photoresist formed of a novolac resin and 1,2-naphthoquinonediazide sulfonate, and a binder and a photoacid generator having a base which causes an alkali dissolution rate to be decomposed by an acid. a chemically amplified photoresist, a chemically amplified photoresist formed by a low molecular compound which is caused by acid decomposition to increase the rate of alkali dissolution of a photoresist, an alkali-soluble binder and a photoacid generator, and an alkali dissolution rate due to acid decomposition A base-based adhesive and a chemically amplified photoresist formed by a low molecular compound and a photoacid generator which are caused by acid decomposition to increase the rate of alkali dissolution of the photoresist. Specifically, for example, the product name: APEX-X (manufactured by Rohm and Haas Electronic Materials (formerly known as Shipley Co., Ltd.), trade name: PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and trade name: SEPR43 0 (Shin-Etsu Chemical Industry ( Stock system) and so on. In the method of forming a photoresist pattern for fabricating a semiconductor manufacturing apparatus of the present invention, exposure is performed by exposure through a reticle for forming a specific pattern. For exposure, KrF excimer laser, ArF excimer laser, etc. can be used. After exposure, Post Exposure Bake can be performed as necessary. The conditions for heating after exposure can be suitably selected from a heating temperature of 80 ° C or 150 ° C, a heating time of 〇 3 minutes or even 60 minutes. The photoresist underlayer film and the semiconductor substrate on which the photoresist film is formed are exposed using a photomask, and then a semiconductor device is manufactured through a development step. The photoresist base film of the present invention forms a photoresist underlayer film which is soluble in an alkaline developer by the action of an acid generated by the photoacid generator contained in the photoresist film upon exposure. After the exposure, the resist film and the photoresist underlayer film were developed together with an alkaline developing solution, and the exposed portion of the photoresist film and the photoresist underlayer film was removed by the alkali solubility -26-201100968. The alkaline developing solution may, for example, be an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, tetramethylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline. An aqueous alkaline solution such as an aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant or the like may be added to the developing solution. The conditions for development can be suitably selected from a developing temperature of 5 ° C or even 50 ° C, a developing time of 〇 10 seconds or even 300 seconds. The photoresist base film formed by forming the composition of the photoresist base film of the present invention can be easily developed at room temperature by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide widely used for photoresist development. The photoresist underlayer film forms a photoresist underlayer film, and can also be used as a layer for preventing interaction between the substrate and the photoresist film, preventing the material used for the photoresist film or generating a substance when the photoresist is exposed to have a negative effect on the semiconductor substrate. The affected layer has a layer which prevents the function of expanding the semiconductor substrate from the material generated by the semiconductor substrate to the upper photoresist film, and a barrier layer for reducing the effect of the photovoltaic effect caused by the dielectric layer. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. [Synthesis of Monomer] -27-201100968 &lt;Synthesis Example 1&gt; 9-hour reaction was carried out by heating 9-anthracene carboxylic acid (Tokyo Chemical Industry Co., Ltd. M 〇g and sulfinium chloride 214 g) while heating under reflux. The reaction was concentrated and azeotroped with toluene followed by drying under reduced pressure to give a mixture of &lt;RTI ID=0.0&gt;&gt; g After dissolving in dichloromethane (128 g), '8 g of the above 9-indole carboxylic acid chloride was dissolved in 68 g of dichloromethane. Then, the reaction was carried out for 3 hours while heating under reflux. Thereafter, by concentration and extraction, Recrystallization was carried out in a mixed solvent of hexane/ethyl acetate to obtain 44 g of 2-vinyloxy-1-(9-fluorenylcarbonyloxy)ethylene represented by the following formula (1 〇).

&lt;Synthesis Example 2&gt; 9-glycosylmethyl 蒽uog, sodium carbonate 42 g, chlorine (丨, 5-cyclooctadiene)-sensitive (1) dimer (Tokyo Chemical Industry Co., Ltd.) 6 g and toluene 1.2 L were Heat at 100 ° C and drip 500 5 g of vinyl acetate. After 丨 回复 回复 回复 回复 回复 回复 回复 回复 回复 回复 回复 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’

&lt;Synthesis Example 3&gt; 50 50 g of 2-naphthocarboxylic acid (Tokyo Chemical Industry Co., Ltd.) and sulfinium chloride were heated to 50 ° C, and the reaction was carried out for 1.5 hours. Thereafter, the reaction was reduced and azeotroped with toluene, followed by drying under reduced pressure to give a carboxylic acid chloride (5 g). Next, 43 g of ethylene glycol monovinyl ether and 81 g of triamine were dissolved in 402 g of dichloromethane under a nitrogen atmosphere. Thereafter, 55 g of the above 2-naphthalene carboxylate was added dropwise to 2 〇Og of dichloromethane. Then, the reaction was carried out by heating under reflux for 3 hours. Thereafter, the mixture was concentrated and extracted, and recrystallized from a mixed solvent of hexane/ethyl ester to obtain 56 g of 2-yloxy-1-(2-naphthalenecarbonyloxy)ethylene represented by the following formula (12). 2〇7g substance 2-naphthalene ethyl acid chloride edge acid ethylene

-29-201100968 &lt;Synthesis Example 4&gt; 36.8 g of methylpropionic acid, 9-genus obtained in Synthesis Example 2; methyl vinyl ether 20 g' 4-methoxyphenol 0.06 g and toluene 85.lg A pyridine gun P-toluenesulfonate 〇_〗 5 g was added to the solution, and the reaction was carried out for 12 hours at room temperature. Thereafter, the mixture was extracted with an aqueous sodium carbonate solution and a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 27.3 g of a methacrylate monomer represented by the following formula (13). [化1 7]

[Synthesis of Polymer] &lt;Synthesis Example 5 &gt; In the solution of poly(4-vinylphenol) l〇.〇g (weight average molecular weight Mw = 15000) (Tosoh (stock)) and tetrahydrofuran (79 g) 20 g of 2-vinyloxy-1-(9-fluorenylcarbonyloxy)ethylene obtained in Synthesis Example 1 and 0. 1 g of 36% by mass hydrochloric acid were stirred at room temperature for 16 hours, and then reacted. Thereafter, the reaction solution was added to 28 mass% aqueous ammonia. Water was added to precipitate the polymer. After the obtained polymer was redissolved in acetone, polymerization was carried out in toluene to precipitate -30-201100968. Then, the polymer was dried under reduced pressure to obtain 23 g of a polymer represented by the following formula (14). With respect to the obtained polymer, it was confirmed by 1 H-NMR analysis that 36% of the phenolic hydroxyl group in the poly(4-vinylphenol) was acetalized (acetal protection).

Ο &lt;Synthesis Example 6 &gt; In a solution of poly(4-vinylphenol) 3.1 g (weight average molecular weight Mw = 15 000) (Tosoh (stock)) and tetrahydrofuran 16 g, the synthesis example 2 was added. 3.8 g of 9-fluorene methyl vinyl ether and O.Olg of 36% by mass hydrochloric acid were stirred at room temperature for 16 hours, and then reacted. Thereafter, after adding 0.8 g of 28% by mass aqueous ammonia to the reaction solution, water was added to precipitate a polymer. After the obtained polymer was redissolved in acetone, the polymer was precipitated with toluene. Then, the polymer was dried under reduced pressure to give 6.4 g of a polymer represented by the following formula (15). -31 - 201100968 With respect to the obtained polymer, it was confirmed by analysis of 1η-nmr that 28% of the phenolic hydroxyl group in the poly(4-ethylidenephenol) was acetalized (acetal protection). [化1 9]

CH (15) &lt;Synthesis Example 7&gt; In a solution of poly(4-vinylphenol) 3.1 g (weight average molecular weight M w = 1 5 000) (Tosoh (stock)) and tetrahydrofuran (19 g), a synthesis example was added. The obtained 2-vinyloxy-; i-(2-naphthalenecarbonyloxy)ethylene 4.9 g and 36% by mass of O.Olg hydrochloric acid were stirred and reacted at room temperature for 47 hours. Thereafter, water of 28 mass% aqueous ammonia was added to the reaction mixture, and water was added to precipitate a polymer. After the obtained polymer was redissolved in acetone, the polymer was precipitated with toluene. Next, this polymer was dried under reduced pressure to obtain 4.0 g of a polymer represented by the following formula (丨6). With respect to the obtained polymer, it was confirmed by 1H-NMR analysis that 40% of the phenolic hydroxyl group in the poly(4-ethlylphenol) was acetalized (acetal protection). -32- 201100968

&lt;Synthesis Example 8&gt; 2-ethylidene obtained in Synthesis Example 3 was added to a solution of poly(4-vinylphenol) 3.1 g (weight average molecular weight Mw = 15000) (Tosoh) and 20 g of tetrahydrofuran. 1-oxyl-l-(2-caxyloxy)ethane i. 5g, 2-vinyloxy-1-(9-fluorenylcarbonyloxy)ethylene obtained in Synthesis Example 4.4g and 36-mass The amount of O.Olg in hydrochloric acid was measured by stirring at room temperature for 36 hours. Thereafter, after adding 0.6 g of 28% by mass aqueous ammonia to the reaction mixture, water was added to precipitate a polymer. After the obtained polymer was redissolved in acetone, the polymer was precipitated with toluene. Then, the polymer was dried under reduced pressure to obtain 5.8 g of the polymer represented by the formula (17) below. With respect to the obtained polymer, it was confirmed by 1 H-NMR analysis that 34% of the phenolic hydroxyl group in the poly(4-ethylphenol) was acetalized (acetal protection). Further, the modification ratio of the protecting group in the acid-reducing protection, naphthalene derivative / anthracene derivative = 24/76 (mole ratio). -33- 201100968 【化2 1】

(17) &lt;Synthesis Example 9&gt; 3.1 g of poly(4-vinylphenol/methacrylic acid = 73.9/26.1 homopolymer) (weight average molecular weight Mw = 15 Å) (Jiushan Petrochemical Co., Ltd. To a solution of 20 g of tetrahydrofuran, 6.2 g of a 2-vinyloxy-1-(9-fluorenylcarbonyloxy) group obtained in Synthesis Example 1 and 36 masses of 〇 〇 〇 〇 〇 After the reaction was carried out for 22 hours at room temperature, the reaction was carried out. Thereafter, after the reaction mixture was added with 28% by mass of ammonia hydrazine·6 g, water was added to kill the polymer. After the obtained polymer was redissolved in acetone, Toluene precipitated the polymer. Next, the polymer was dried under reduced pressure to obtain 4.1 g of the polymer represented by the following formula (18). About the obtained polymer, it was confirmed by 13c-nmr to confirm the phenolic hydroxyl group 23 %, 19% of the carboxyl group is acetalized (protected by acetal). -34- 201100968 [Chem. 2 2]

&lt;Synthesis Example 1〇&gt; 4.5 g of 9-fluorene methyl methacrylate, 15 g of 4_z nonyloxystyrene, and 1.2 g of 2,2,-azobis(isobutyric acid) dimethyl ester were dissolved in 2- After 31 g of butanone, the solution was allowed to drip for 2 hours to 2 to butyl 252 g and heated to reflux in a beaker. Thereafter, the mixture was heated under reflux for 12 hours, and then returned to room temperature, and a solution obtained by hydrazine was added to hexane to give a white powder of 10.5 g of a polymer represented by the following formula (19).

-35- 201100968 Next, the polymer l〇g represented by the above formula (19) and triethyl cumene l〇g were dissolved in 5 g of water, 30 g of methanol and 3 g of tetrahydrofuran. Thereafter, after heating for 5 hours, the mixture was returned to room temperature, and the resulting solution was added to water. Thereafter, it was redissolved in tetrahydrofuran, and then added to diethyl ether to obtain a pale brown powder of the polymer i.lg represented by the following formula (20). [Chem. 2 4]

&lt;Synthesis Example 1 1 &gt; 5.17 g of 4-phenylphenylmethyl decylamine, 4 g of acetal monomer represented by the formula (13) obtained in Synthesis Example 4, 2,2, azobis ( A solution of isobutyric acid) dimethyl ester 〇. 55 g and tetrahydrofuran (43.9 g) was heated under reflux to carry out a reaction for 1 hour. Thereafter, the polymer was precipitated using acetonitrile, and the polymer was dried under reduced pressure to give a polymer of the following formula (2): 〇g. The weight average molecular weight of the polymer obtained from &amp; is 1.6,200 in terms of standard polystyrene. -36- 201100968

G &lt;Synthesis Example 12&gt; 4.99 g of 4-hydroxyphenylmethacrylamide, 4 g of 9-methylmethyl propyl acrylate, 2,2,-azobis(isobutyric acid) dimethyl ester 〇 A solution of .60 g and tetrazolium 47.3 5 g was heated under reflux for 1 hour reaction. Thereafter, the polymer was precipitated using acetonitrile, and the polymer was dried under reduced pressure to obtain 8.2 g of the τρς polymer represented by the following formula (22). The weight average molecular weight of the obtained polymer is 13,000 标准f 2 6

(22) Embodiments 1 to 5 are examples corresponding to the first aspect of the present invention, and -37-201100968 Comparative Example 1 is a comparative example corresponding to the first aspect of the present invention. Further, Example 6 is an embodiment corresponding to the second aspect of the present invention. Comparative Example 2 is a comparative example corresponding to the second aspect of the present invention. &lt;Example 1&gt; In the polymer 〇.2g obtained in Synthesis Example 5, the above formula (8) was mixed with q = 4 to represent 1,3,5-tris(4-vinyloxybutyl)trimethylene oxide. 0.04 g of tricarboxylic acid and triphenylsulfonium P-toluenesulfonate 〇.〇〇4§, and dissolved in propylene glycol monomethyl ether l〇g into a solution. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore diameter of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 〇·05 to prepare a composition (solution) of the photoresist underlayer film. &lt;Example 2 to Example 5&gt; In the same manner as in Example 1, 0.2 g of the polymer obtained in Synthesis Example 6 to Synthesis Example 9 was mixed with 1,3,5-tris(4-vinyloxybutyl) three. 0.04 g of trimellitic acid and 4 g of triphenylsulfonium p-toluenesulfonate were dissolved in propylene glycol monomethyl ether to obtain a solution. Thereafter, it was filtered using a polyethylene microfilter having a pore size of Ο.ΙΟμιη, and further filtered using a polyethylene microfilter having a pore size of 〇. 5 μηι to prepare a composition (solution) of the photoresist underlayer film. Using the polymer-formed photoresist underlayer film obtained in Synthesis Example 6 to form a composition (solution) corresponding to Example 2, using the polymer-treated photoresist underlayer film obtained in Synthesis Example 7 to form a composition (solution) corresponding to Example 3, Using a polymer-treated photoresist underlayer film obtained in Example 8 to form a composition (solution) corresponding to Example 4' using the polymer-treated photoresist underlayer film obtained in Synthesis Example 9 to form a composition (solution) Corresponding Example 5 » &lt;Example 6&gt; In 0.4 g of the polymer obtained in Synthesis Example 11, 1,3,5-tris(4-vinyloxybutyl)trimethylenetricarboxylic acid ruthenium ruthenium was mixed. 8 g and p-toluenesulfonate 〇〇. 2 g were dissolved in 18 g of propylene glycol monomethyl ether to prepare a solution. Thereafter, it was filtered using a polyethylene microfilter having a pore size of 0.10 μm, and then filtered using a polyethylene microfilter having a pore size of 〇·〇5 μm to prepare a composition (solution) of the photoresist underlayer film. &lt;Comparative Example 1&gt; In the same manner as in Example 1, 0.2 g of the polymer obtained in Synthesis Example 10 was mixed with 1,3,5-tris(4-vinyloxybutyl)trimellitic acid ruthenium. 4 £ and Ο Triphenyl mirror P-toluenesulfonate 〇. 4g, and dissolved in propylene glycol monomethyl ether l〇g into a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 〇.1〇μηη, and further filtered using a polyethylene microfilter having a pore size of 〇.5 μιη, and then a photoresist base film was formed to form a composition (solution). . &lt;Comparative Example 2 &gt; In the polymer 〇.4g obtained in Synthesis Example 12, 1,3,5-tris(4-vinyloxybutyl)trim trimellitic acid 〇.〇8g and P were mixed. 2-toluenesulfonate 〇. 2 g, which was dissolved in 18 g of propylene glycol monomethyl ether to prepare a solution. After -39-201100968, it was filtered using a polyethylene microfilter having a pore size of 0.1 〇μιη, and then filtered using a polyethylene microfilter having a pore size of 〇.5 μηι to prepare a photoresist underlayer film to form a composition (solution). . [Dissolution test for photoresist solvent] Each of the photoresist base film prepared in Example 1 to Example 6, and Comparative Example 1 and Comparative Example 2 was formed into a composition (solution) as a spin coater on a semiconductor substrate (矽Wafer) coated. Thereafter, baking was performed for 1 minute on a hot plate of 160 t to form a photoresist underlayer film [film thickness 〇·6 μm (the film thickness of Example 6 and Comparative Example 2 was 0.05 μm)]. The photoresist underlayer film is immersed in a solvent used for the photoresist, for example, propylene glycol monomethyl ether. As a result, it was found to be insoluble in the solvent. [Test of optical parameters] Each of the photoresist base film formed in Example 1 to Example 6, and Comparative Example 1 and Comparative Example 2 was formed into a composition (solution) by a spin coater on a semiconductor substrate (twisted crystal) Round). Thereafter, baking was performed on a hot plate at 160 ° C for 1 minute to form a photoresist underlayer film [film thickness 〇 〇 6 μϊη (the film thickness of Example 6 and Comparative Example 2 was 0.05 μm)]. Next, the photo-resistive underlayer film is measured by a light elliptical thickness gauge (JAWoollam Gong 3 0 2 ), and the refractive index (η値) and attenuation coefficient (k値) of the wavelengths of 248 nm and 193 nm are measured. . The results are shown in Table 1. -40- 201100968 [Table l] — U·8 nm 193 nm Refractive index (η値) Attenuation coefficient (k値) Refractive index (η値) Attenuation coefficient (k値) Example 1 1.60 0.42 1.78 0.35 Example 2 1.63 0.43 1.60 0.85 Example 3 2.00 0.24 1.87 0.34 Example 4 1.68 0.35 1.55 0.63 Example 5 1.68 0.42 1.58 0.65 Example ό 1.51 0.41 • Comparative Example 1 1.59 0.27 1.54 0.62 Comparative Example 2 1.51 0.42 - _ The results shown in Table 1 ' It is understood that the photoresist underlayer film obtained by forming the composition of the photoresist underlayer film of the present invention has a sufficiently effective refractive index and attenuation coefficient for light of 248 nm and 193 nm. [Evaluation of Pattern Shape] Each of the photoresist underlayer films prepared in Example 4 and Comparative Example 1 was formed into a composition (solution) by a spin coater and coated on a semiconductor substrate (tantalum wafer). Thereafter, baking was performed on a hot plate at 200 ° C for 1 minute to form a photoresist underlayer film (film thickness 〇. 5 μιη). On the photoresist underlayer film, a commercially available photoresist solution (manufactured by JSR Co., Ltd., trade name: V146G) was applied by a spin coater and heated on a hot plate at 1 〇 ° C for 60 seconds. After that, a photoresist film was formed (film thickness: 0·425 μπ〇. Then, an ASM750 scanner (wavelength: 248 nm, ΝΑ: 0.70, σ: 0.8 75/0.575 (ANNULAR)) manufactured by ASML Co., Ltd. was used, and the developed photoresist pattern line was developed. The width and the width between the lines become the mask set by the method of 1 8 μηι, and the exposure is performed. Thereafter, 60 seconds of "heating after exposure" is performed on a hot plate at 110 ° C. After cooling, the developer is cooled. Development was carried out using an aqueous solution of tetra-41 - 201100968 methyl ammonium hydroxide as defined in Japanese 0.26. After development, the obtained resist pattern profile was observed by a scanning electron microscope (SEM). As a result, the light modulated in Example 4 was used. When the underlayer film is formed into a composition (solution), the shape of the obtained photoresist pattern has a good straight line shape as shown in Fig. 1, and has no residue. Further, the composition of the photoresist underlayer film prepared in Comparative Example 1 is used to form a composition. When the solution (solution), part of the photoresist underlayer film is not Development and residue. [Evaluation of developability] Each of the photoresist base film prepared in Example 6 and Comparative Example 2 was formed into a composition (solution) by a spin coater and applied onto a semiconductor substrate (tantalum wafer). Thereafter, baking was performed on a hot plate at 160 ° C for 1 minute to form a photoresist underlayer film (film thickness 〇 5 μm η), followed by full exposure with an exposure machine (wavelength 248 nm), and after 60 seconds of exposure, 11 (heating on a hot plate of TC for 60 seconds. After cooling, the developing solution was developed using an aqueous solution of tetramethylammonium hydroxide specified in Japanese 0.26. As a result, the composition was formed using the photoresist underlayer film prepared in Example 6 ( In the case of the solution, all of the solution was dissolved in the developer. Further, in Comparative Example 2, there was a residual film of 0.02 μm after development. [Schematic Description] [Fig. 1] Fig. 1 shows the formation of the photoresist underlayer film prepared in Example 4. SEM image of the resist pattern obtained after development in the composition (solution)-42-

Claims (1)

201100968 VII. Patent application scope: 1. A photoresist base film forming composition comprising (A) component, (B) component and solvent, (A) component: a structural unit represented by the following formula (1) a polymer having a weight average molecular weight of 1,000 to 200,000 (B) Component: a crosslinkable compound Q (wherein Ri is a hydrogen atom or a methyl group 'R2 is a hydrogen atom or a group having 1 or 3 carbon atoms, R3 is a hydrogen atom or a methyl group, p is a divalent organic group, and Q is an unsubstituted naphthalene ring. Or an anthracene ring or a naphthalene having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a halogen atom, a fluorenyl group, an amine group, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Ring or ring). 2. The photoresist base film forming composition of claim 1, wherein the divalent organic group P is a group represented by the following formula (2) or formula (3), or a hydrocarbon having a carbon number of 1 or 10; Base, -43- (2) 201100968 [Chemical 2] Ο [In equations (2) and (3), 111 and n are each an integer of 1 or even an integer] 〇 3. The light of claim 1 or claim 2 The underlayer film forming composition 'wherein the polymer of the component (A)' is a structural unit other than the structural unit represented by the above formula U), and has a structural unit represented by the following formula (4): 3 λ V (wherein R4 is a hydrogen atom or a methyl group). 4. The photoresist base film forming composition of any one of Claims 1 to 3, wherein the polymer of the above (Α) component further has a structural unit represented by the following formula (5), R5 1 (X (5) -44- 201100968 (wherein Rs is a hydrogen atom or a methyl group, X is an alkyl group having 1 or 10 carbon atoms or a phenyl group, and k is the number of groups represented by X, k is 0 or 1, but when k is 0, the carboxyl group is directly bonded to the main chain.) The photoresist base film forming composition according to any one of claim 1 or claim 4, wherein the photoacid is further produced 6. The photoresist base film forming composition of claim 5, further comprising a basic compound. Ο 7. A photoresist base film forming composition characterized by containing (A') component, (B) Component and solvent, (A') component, polymer (B) having a weight average molecular weight of 1,000 to 200,000 of a structural unit represented by the following formula (6): a crosslinkable compound (wherein, Ri is a hydrogen atom or a methyl group, R6 is a benzene ring or a direct bond, and P is a divalent organic group, Q is an unsubstituted naphthalene ring or an anthracene ring or has a terminal selected from a hydroxyl group, a carboxyl group, or a halogen atom. a sulfonyl group, an amine group, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms or an alkyl group in which the aryl group is a group of at least one substituent -45-201100968 naphthalene ring or anthracene ring). 8. The photoresist base film forming composition according to claim 7, wherein the above-mentioned divalent organic group P is an alkylene group having 1 to 10 carbon atoms. 9. The photoresist base film forming composition of claim 7 or claim 8, wherein the polymer of the component (A') has the following formula as a structural unit other than the structural unit represented by the above formula (6); (7) The structural unit represented, [Chem. 6] Wherein R7 is a hydrogen atom or a methyl group, j is hydrazine or l, and when j is 0, a phenyl group having a hydroxyl group as a substituent is directly bonded to the main chain, and when j is 1, A is -C ( = 0) -NH-group or -(:(=0)-0-yl}. 10. The photoresist base film forming composition according to any one of claim 7 to claim 9, wherein the aforementioned (A' a polymer of the component, which further has a structural unit represented by the following formula (5), COOH 201100968 (wherein Rs is a hydrogen atom or a methyl group, χ is a number of atoms or even a quinone of a phenyl group, and k is a number represented by X, k is 〇 or 1, but ' When k is 0, the carboxyl group is directly bonded to the main chain). The photoresist underlayer film forming composition according to any one of claim 7 or claim 1, wherein the photoacid generator is further contained. 1 2. The photoresist base film forming composition of claim 1 wherein 〇 further contains a basic compound. 13. A method for forming a photoresist pattern for fabricating a semiconductor device, comprising: coating the photoresist underlayer film forming composition of any one of claim 1 or claim 12 on a semiconductor substrate, and a step of baking to form a photoresist underlayer film, a step of forming a photoresist film on the photoresist underlayer film, and a step of exposing the photoresist underlayer film and the semiconductor substrate covered by the photoresist film The step of developing the photoresist film and the photoresist underlayer film after exposure. -47-