TW201028795A - Positive photoresist composition and process for formation of photoresist pattern using the same - Google Patents

Abstract

The present invention provides a positive photoresist composition capable of excellently maintaining the adhesion between a photoresist film and a substrate for forming a micro photoresist pattern and inhibiting the amount of scum produced by the photoresist film after development, and also provides a process for formation of photoresist pattern using the same. The positive photoresist composition includes: (A) alkali-soluble novolac varnish resin; (B) sensitizer; and specific (C) benzotriazole compound. Because of containing the specific benzotriazole compound, the present invention is able to maintain an excellent adhesion between the photoresist film and the substrate for forming the micro photoresist pattern, and also inhibits the amount of scum even after the photoresist film has been developed.

Description

201028795 VI. [Technical Field] The present invention relates to a positive-type photoresist composition capable of forming a fine photoresist pattern and having a small amount of residue generated after development of a photoresist film, and a composition using the same A method of forming a photoresist pattern. [Prior Art] A technique (pattern forming technique) of forming a fine pattern on a substrate and etching it as a mask to form a lower layer of the pattern or forming wiring by plating Techniques such as "wiring" and "bump" have been widely used in the manufacture of integrated circuit circuits in the semiconductor industry, and have received great attention. Among them, regarding the pattern forming technique, the fine pattern is usually composed of an organic material, and is subjected to techniques such as lithography (meth) or nano-imprint meth〇d. form. The lithography method is a method of forming a photoresist film made of a photoresist composition containing a resin or the like on a support such as a substrate, and then interposing a mask (mask pattern) through which a predetermined pattern is formed. And the photoresist film is irradiated with actinic rays such as light or electron rays to selectively expose the film, and a development process is applied to form a photoresist pattern of a predetermined shape on the photoresist film. In the case of a photoresist film, the exposed portion is changed to have a photoresist composition which is soluble in the developer, and is called a "positive photoresist composition", and the exposed portion is changed to have a The photoresist composition of the characteristics dissolved in the developer is referred to as a "negative photoresist composition". 201028795 In recent years, portable thunder & digital cameras and other electronic broadcasts, such as sputum, criminalization and lightweighting, have been developed in the small size of the machine and have been developed in the previous packaging technology.

System in p , \ Extension line SiP (system-in-package: p , . — SP (wafer size package: chip Size

Package). The CSP is y. For the size of the wafer-level, it must be wired on the upper part of the wafer, and the wiring pitch (wiring pitch) is required. The formation of the wiring is mainly achieved by patterning the photoresist and then performing a steel recording or a copper etching along the photoresist pattern, because of the finer wiring pitch and the higher resolution of the photoresist. It is indispensable. Based on these backgrounds, the demand for high resolution of photoresist patterns from the market has increased. Further, as the photoresist composition is highly resolved, the contact area between the photoresist pattern and the substrate is reduced, and the substrate adhesion is also required to be improved. If the adhesion is poor, there is a problem in that the photoresist pattern is peeled off during development, etching or plating. (Measures for improving the adhesion of the substrate) A method of using a benzotriazole or the like to enhance the sputum is known (see, for example, Patent Document 1). [Previous Technical Literature] (Invention Patent Document) (Invention Patent Document 1) 曰 Patent Application Laid-Open No. 2008 158157 [Summary of the Invention] [Technical Problem to be Solved by the Invention] 4 201028795 However, 'previous additive (closed) The reinforcing agent) has to bear the problem that the residue due to the photoresist film remains as a residue (scum·scum) after development and remains between the photoresist patterns, and serves as a photoresist pattern and the adhesion of the substrate. Get the price of improvement. The present invention has been developed in view of the above-described technical problems, and an object thereof is to provide a positive-type photoresist composition which can well maintain the adhesion of a photoresist film to a substrate to form a fine photoresist pattern, and also It is possible to suppress the generation of residue of the photoresist film after development, and to provide a method for forming a photoresist pattern using the composition. [Technical means for solving the problem] The inventors of the present invention have found that an alkali-soluble novolac resin (&1) The positive resistive composition of the agent and the specific benzotriazole-based compound can solve the technical problems as described above and finally complete the present invention. Specifically, the present invention provides the following. The first aspect of the invention of Lu Wei is a positive-type photoresist composition comprising: (A) an alkali-soluble novolac resin, (B) a sensitizer, and (c) a benzodiazole-based compound, and the benzene The triazole compound is a compound represented by the following formula (1): [Chemical Formula 1] 5 201028795

[In the formula (D, F·1 is an alkyl group having a carbon number of 1 or more and 10 or less, a hydroxyl group, a thiol group, an donor atom, or a COOR' (R' is a carbon number of 1 or more and 5 or less. R2 and R3 are each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 or more and 6 or less, or a Φ hydroxyalkyl group having a carbon number of 1 or more and 6 or less, but selected from the group 2 and r3. At least one of them is a hydroxyalkyl group having a carbon number of 1 or more and 6 or less.] The second aspect of the present invention is a positive-type photoresist composition comprising: (A') hydrogen possessed by a phenolic hydroxyl group At least a portion of the atom is replaced by a ruthenium, a 2-naphth〇quinonediazidesulf〇nyl gr〇up, a soluble varnish resin, and (c) a benzotriene a lanthanide compound' and the benzotrisal compound is a compound represented by the following formula (1): ® [Chemical 2]

[In the general formula (1), 'R1 represents a carbon number of 1 or more and is an alkyl group, a thiol group, a thiol group, a hydrogen atom, or a —c〇〇R, (R is a carbon number of up to 5 or less. HR3 is independently represented by hydrogen 6 201028795 An alkyl group having a carbon number of 1 or more and 6 or less, or a hydroxyalkyl group having a carbon number of 丨 or more and 6 or less, but at least one selected from the group consisting of R 2 and R 3 is carbon The number is a hydroxyalkyl group of i or more and 6 or less. ]. A third aspect of the present invention is a method for forming a photoresist pattern comprising the steps of: coating a positive photoresist composition of the present invention on a substrate to obtain a "coating step" of the photoresist film; An "exposure step" of exposing the photoresist film to actinic radiation; and a development step of obtaining a photoresist pattern after the exposure step. • [Effects of the Invention] According to the positive-type photoresist composition of the present invention, since the positive-type photoresist composition is a benzotris-based compound, the adhesion between the photoresist film and the substrate can be Maintaining a good condition allows a fine photoresist pattern to be formed, and at the same time, the amount of residual fishing can be suppressed to a small amount even after development of the photoresist film. [Embodiment] [Best Mode for Carrying Out the Invention] The following is a description of the preferred embodiments of the present invention in more detail. <Positive-type photoresist composition> The positive-type photoresist composition of the first aspect of the invention comprises: (A) a soluble secret varnish resin (hereinafter referred to as "(A) component") (B) a sensitizer, and a specific (c) benzotriazole-based compound. Further, the positive-type photoresist composition of the second aspect of the present invention is characterized in that it contains 201028795: at least a part of the hydrogen atom possessed by the (A') hydroxy group is a 1,2-naphthalene-doped azide sulfonate. An alkali-soluble novolac resin (hereinafter referred to as "(A') component)" and a specific (C) benzotrizene compound which are substituted by a mercapto group. [(A) alkali-soluble novolak resin] The "(A) component" contained in the positive-type photoresist composition of the first aspect of the invention is not particularly limited, but preferably has phenolic property. The aromatic compound (hereinafter, simply referred to as "phenol") and the aldehyde are obtained by addition condensation in the presence of an acid catalyst. (Phenols) As described above, "the class J" includes, for example, "cresols" such as phenol, o-cresol, m-cresol, p-cresol, etc.; 2,3_nonanol, 2 , 4-nonanol, 2,5-nonanol, 2,6-nonanol, 3,4-nonanol, 3,5-nonanol, etc. "indophenol"; o-ethylphenol, m-ethylphenol , p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p-tert-butylphenol, etc. "Alkylphenols"; "trialkylphenols" such as 2,3,5-trimethylphenol and 3,4,5-tridecylphenol; resorcinol, catechol (o-phenylene) "polyphenols" such as phenol), hydroquinone, hydroquinone, mercapto, fluoroglycol, etc.; alkyl resorcinol, alkyl catechol, alkyl hydroquinone, etc. "Alkyl polyphenols (wherein any alkyl group has a carbon number of 丨 or more and 4 or less)"; ?-naphthol, cold-naphthol, hydroxybiphenyl, bisphenol a, and the like. These may be used singly or in combination of two or more thereof. 201028795 Among the above categories, it is better to have a squad and a pair of cresols. More preferably, it is a combination of m-cresol and p-cresol. In this case, many characteristics such as sensitivity and heat resistance of the positive resist composition can be adjusted by adjusting the blending ratio of the two. There is no particular limitation on the ratio of m-cresol to p-cresol, but it is preferably 3/7 or more and 8/2 or less (mass ratio) based on the ratio of m-cresol/p-phenol. By setting the ratio of m-cresol to 3/7 or more, the sensitivity can be improved, and by setting it to 8/2 or less, heat resistance can be improved. (Plastic) "Aldehyde" includes, for example, 'formaldehyde, polyacetal, furfural, benzotriene, succinylbenzene, and ethylene. These may be used singly or in combination of two or more kinds thereof. (Acid Catalyst) "Acid catalyst" includes, for example, "inorganic acids" such as 'hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and argon acid; formic acid (formic acid), oxalic acid (oxalic acid), and acetic acid (acetic acid); "Organic acid" such as monoethyl sulphate or p-toluene sulphonic acid; zinc acetate is considered to be "the metal salt of Sisui Temple". These acid catalysts may be used singly or in combination of two or more. (Molecular weight) The mass average molecular weight of the (Α) component is preferably made from the viewpoint of developability, analytical properties, and piating section resistance of the positive resist composition. Above and below 50,000 (classification treatment) (A) component is preferably reduced by the classification treatment (^α〇ηαΗ〇η 201028795 treatment ) to the content of the low polymer to 80% by mass or less before the classification treatment, More preferably, it is a fractionated resin obtained by 5% by mass or less. The term "lower oligomer" as used herein means a phenol which is as described above, that is, a phenolic monomer, and a dimer obtained from the phenolic monomer of two molecules, and is composed of three molecules. a terpolymer obtained from the phenolic monomer or the like. By using such a graded resin, the perpendicularity of the cross-sectional shape of the photoresist pattern can be further improved, and the photoresist residue (scum) is less likely to be generated during development, and the high resolution can be improved. Become a person with superior heat resistance. The classification treatment ' can be carried out by, for example, the following fractional precipitation treatment. First, as described above, after the addition and condensation reaction of the mixture and the compound, the obtained addition condensation product (the varnish resin) is dissolved in a polar solvent, and water, heptane, and hexane are added to the solution. , poor solvent such as pentane or cyclohexane. At this time, since the low polymer is so high in solubility that it is still dissolved in a poor solvent, the fractionated resin which is reduced in the low polymer content can be obtained by taking the precipitate. The "polar solvent" as described above includes, for example, "alcohols" such as decyl alcohol and ethanol; "anthracene" such as acetone or methyl ethyl ketone; and ethylene glycol monoethyl ether acetate. "Glycol ether esters"; "cyclic ethers" such as tetrahydroanthracene. The content of the low polymer in the component (A) can be confirmed by the results of Gpc (coagulation). That is, the molecular weight distribution of the synthesized phenol novolac resin (phen〇1 novolac resin 10 201028795 ) can be confirmed from the Gpc chart, and by measuring the intensity ratio of the peak of the elution time of the low polymer, Then the content can be calculated. In addition, since the elution time of the low polymer is different depending on the measurement system used, the column, the eluent, the flow rate, the temperature, the detector, the sample concentration, the injection amount, and the measuring device are different. It is important to be specific. The degree of dispersion (mass average molecular weight (Mw) / number average molecular weight (?η)) of the scalloped tree, preferably 30 or less, more preferably 15 or more and 25 or less. Luke [(Α') phenolic hydroxyl group has at least a part of a hydrogen atom which is substituted by an alkali-soluble novolac resin substituted with 2-naphthoquinonediazidesulfonyl]. In the second aspect of the present invention The "(Α) component" contained in the positive resist composition is not particularly limited, but is preferably one of the hydrogen atoms of all the phenolic hydroxyl groups contained in the (Α) component as described above. The portion 'is replaced by a 1,2-naphthalene-dopedazidosulfonyl group. When the (a') component is used, since the naphthoquinonediazidesulfonyl group having a small (Α) component itself is photosensitive, the sensitivity of the positive photoresist composition can be further improved. The substitution with the 1,2-naphthoquinonediazidesulfonyl group can be carried out by an esterification reaction of the (α) component with a 1,2-naphthoquinonediazidesulfonic acid compound. "丨, 2_naphthoquinonediazidesulfonic acid compound" includes, for example, hydrazine, 2_naphthoquinonediazide-4-sulfonic acid vapor, 1,2-naphthoquinonediazidesulfonic acid vapor, and the like. "The composition of the bismuth gas compound". In the (Α') component, the ratio of the hydrogen atom of the desired hydroxyl group to the naphthoquinone diazidesulfonyl group, that is, the reaction rate of the esterification reaction is 201028795, preferably 2 mol%. The above is more than 10% by mole of the tile, more preferably 3 moles or more, more preferably 3 moles or more and more than 5 2 moles, and it is possible to suppress the unexposed mole % or less, thereby improving the sensitivity, and the same percentage or more. And 7 moles. /❶ Below, Moer% or less. If the reaction rate is a partial film reduction, and if it is 1 可使, the perpendicularity of the cross-sectional shape of the photoresist pattern tends to be good. [(B) Photosensitive Agent] The "sensitizer" contained in the positive resist composition of the present invention is not particularly limited, but is preferably a compound containing a quinonediazide group. • The "compound containing a quinonediazide group" includes, for example, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6 Hydroxybenzophenone, 2,3,6·trihydroxybenzophenone, 2,3,4-trihydroxy-2,-methylbenzhydryl, 2,3,4,4,-tetrahydroxy Benzophenone, 2,2',4,4,tetrahydroxydiphenylhydrazine, 2,3',4,4',6-pentahydroxydiphenylhydrazine, 2,2',3,44,pentahydroxyl Benzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3,,4,4,5,6-hexahydroxybenzophenone, 2,3,3 ',4,4,,5'_hexahydroxybenzophenone and other "polyhydroxydibenzophenones"; bis(2,4-dihydroxyphenyl)decane, double (2,3,4_ Trisylphenyl)methane, 2_(4-hydroxyphenyl)-2-(4,-hydroxyphenyl)propyl, 2-(2,4-dihydroxyphenyl)_2_ (factory/dihydroxy) Phenyl)propane, 2-(2,3,4-trihydroxyphenyl)_2_(2',3,4,3-trihydroxyphenyl)propane, 4,4'- { 1-[ 4-[2_ (4-Hydroxyphenyl)-2-propyl]phenyl]ethylidene} two-year-old, 3,3,-dimethyl-"·[4_[2_(3_methyl_4hydroxyphenyl) -2- "bis[(poly)hydroxyphenyl]-burning", bis(4-phenylphenyl)-methyl, bis (4-_yl)-3,5- Dimethylphenyl)-4-hydroxyphenylnonane, bis(4-hydroxy-25-didecylphenyl 12 201028795 )-4-hydroxyphenylmethane, bis(4-hydroxy-3-3_dimethyl Phenyl)_2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)_2-hydroxyphenylnonane' bis(4-hydroxy-2,5-dimercapto) _3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc. Its methyl substitution"; bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, double (3_cyclohexyl_4_hydroxyphenyl)-4_hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-indolylphenyl)_2·hydroxydecylphenyl decane, double (5 ·cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, double (3-cyclohexyl-2-hydroxyphenyl)- 3-hydroxyphenylmethane, bis(5-cyclohexyl-4-yl-3-methylphenyl)-4-pyridylphenyl, bis(5-cyclohexyl-4-hydroxy_3_A Phenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-indolylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl) )-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenyldecane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl) "Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane such as 2-hydroxyphenylmethane or bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane Class or its methyl substitution"; phenol, p-methoxybenzene, dimercaptobenzene, hydrogen brewing, naphthol (naphthol), pyrogallol (catechol), gallnut Phenol, gallnut age monomethyl ether, gallicol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4,-diaminobenzophenone, etc. a compound of a hydroxyl group or an amine group; a varnish, a gallnut-acetone resin, a light-weight styrene-based 13 201028795 polymer, a copolymer with a copolymerizable monomer, etc.; and a chasing _12 _昼II-based-5-sulfonic acid, naphthoquinone·1,2-diazido-4-sulfonic acid, ortho-infrared dioxane A partial vinegar compound, a amide compound, or a partial amide compound containing a monobasic nitrogen-based continuous acid. These salting agents may be used singly or in combination of two or more. Among these sensitizers, a "quinonediazide sulfonic acid series" of a compound represented by the following formulas (Β4) and (Β-2) is preferred. [North 3]

[In the general formulae (Β-1) and (Β_2), R1 to R7b are each independently represent a hydrogen atom, the carbon number which may have a substituent is 1 or more, or may have a substituent. The compound having a carbon number of 4 or more and 8 or less and cycloalkyl group 14 201028795 (B-2) is particularly excellent among the above-mentioned formula (Β-l) and azeodidinate. It is a brewed diazide vinegar which is a compound represented by the chemical formula (B) shown below. 〔化4〕

Among them, the naphthoquinone sulfonate of the formula represented by the above formula (B_1:) and (Β·2), and the compound represented by the formula (Β-3), naphthoquinone-1,2-diplex The nitrogen-sulfonyl group is preferably a sulfonyl group bonded to the 4- or 5-position φ. When these compounds are used as a solution, the compound can be sufficiently dissolved in a solvent which is generally used, and has good compatibility with a (Α) component or a (Α') component, and is used as a positive type. When the sensitizer of the photoresist composition exhibits high sensitivity and has excellent image contrast and cross-sectional shape, it also has excellent heat resistance, and when used as a solution, it is also available. A positive photoresist composition produced by foreign matter. The "compound represented by the formula (Β-l)" as shown above is, for example, 1-hydroxy-4-[l,l-bis(4-hydroxyphenyl)ethyl]benzene and naphthoquinone-l,2 - 15 201028795 A stack of gas bases - in the presence of diethanolamine, alkali carbonate Condensation is carried out to produce a complete esterification or partial esterification. Further, as the above, "the compound represented by the formula (B-2)" is, for example, ^[丨彳'-p-phenylphenyl)isopropyl]-4-[ 1, 丨_bis(4-hydroxybenzene) Ethyl]benzene and naphthoquinone-1,2-diazido-sulfonium gas are condensed in a solvent such as dioxane and in the presence of a base such as triethanolamine, carbonic acid, hydrogencarbonate or the like. It is made by φ full esterification or partial esterification. Further, "naphthoquinone-1,2-diazide-sulfonyl" is preferably naphthoquinone-1,2-diazido-4_sulfonate or naphthoquinone 4,2-di Azidosulfonate. When the component (a) is used as the base resin, it is preferably used in an amount of 5 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the component (A). More preferably, it is used. 1 part by mass or more and 50 parts by mass or less. When the content is 5 parts by mass or more, it is possible to obtain a photoresist pattern which is desired, and if it is 100 parts by mass or less, a sufficient sensitivity can be obtained. On the other hand, when the matrix resin is used as the (A,) component, although the sensitizer is not an essential component, it is preferred to use a sensitizer, phase leaf + 100 parts by mass of the (A') component. It is used in an amount of 30 parts by mass or less, more preferably 5 parts by mass or more and 2 parts by weight or less. 〔 [(C) benzotrisole compound] 16 201028795 The "benzotrimethane compound" contained in the positive-working photoresist composition of the present invention is represented by the following general formula (1). 〔化5〕

An alkyl group, a hydroxyl group, a carboxyl group, a hydrogen atom, or a COOR, (R is a stilbant having a carbon number of 1 or more and 5 or less); R2 and R3 each independently represent a hydrogen atom, and the carbon number is 1 or more. 6 or less of the alkyl group or the base group having 1 or more and 6 or less carbon atoms, but at least one selected from the group consisting of R2 and R3 is a mercapto group having a carbon number of 1 or more and 6 or less. ]. When the positive-type resist composition contains the benzotriazole-based compound represented by the above formula (1), the adhesion between the photoresist film and the substrate can be maintained well, and a fine photoresist pattern can be formed while After the development of the photoresist film, ® can also suppress the amount of residue generated into a small amount. Here, the alkyl group having a carbon number of R1 of 1 or more and 10 or less is not particularly limited, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an anthranyl group, and an anthracenyl group. In the positive resist composition of the present invention, Ri is preferably an alkyl group having a carbon number of 1 or more and 3 or less, more preferably a methyl group. The "alkyl group having a carbon number of 1 or more and 6 or less" as R2 and R3 includes: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary butyl group, tertiary butyl group, and positive group. Further, "heptyl group, n-hexyl group, etc.", "the number of carbon atoms is 1 or more, and the number of hydroxyalkyl groups of 6 to 28,28,795 and 6 or less" includes: replacing at least one hydrogen atom in the alkyl group having 1 or more and 6 or less carbon atoms The base of the hydroxyl group. As described above, at least one selected from the group consisting of R2 and R3 is a hydroxyalkyl group having a carbon number of 1 or more and 6 or less. When R2 or R3 has a hydroxyalkyl group as described above, the solubility of the benzotriazole-based compound as described above for the positive-type photoresist composition can be sufficiently maintained, and therefore, the positive-type photoresist composition can be sufficiently maintained. The adhesion between the object and the substrate. R2 and R3 are preferably a hydroxyalkyl group having a carbon number of 1 or more and 6 or less, more preferably a 2-hydroxyethyl group.

Specifically, it is preferred to use the benzotriazole-based compound represented by the following "chemical formulae (C-1) to (C-4)". [6]

• · · (C-1)

• · - ( C — 2 )

CH2CH2OH . « .(C _ 4) 18 201028795 B "The benzotriazole compound represented by the formula (1)" can be produced, for example, by the method shown below (see, for example, the patent special opening) Bulletin 2000_044549). The mouth is added with methyl 1H benzotriazole, such as a compound represented by the chemical A (2), a secondary alcohol amine such as diethanolamine, and formaldehyde, as shown in the molar ratio of 1:1:1. The reaction was carried out under reflux of sterol for 5 hours. After the reaction, methanol and water are removed by steaming, whereby the purpose can be obtained. [化7] °

% / H (2) [In the formula (2), R1 is the same as described above. ]. The benzotriazole-based compound represented by the above formula (1) is preferably added in an amount of 0.1 part by mass or more and 5 parts by mass based on 100 parts by mass of the component (A) or the component (A). In the following, it is more preferable to add 2 parts by mass or more and 2 parts by mass or less. When the amount of the benzotriazole-based compound is 0.1 part by mass or more, the adhesion between the photoresist film obtained by the positive-type resist composition of the present invention and the substrate can be sufficiently increased. Further, the amount of the benzotriazole-based compound added is 5 parts by mass or less. After the development of the photoresist film as described above, a favorable photoresist pattern having less residue can be obtained. [(D) Sensitizer] The positive-type photoresist composition of the present invention may contain a sensitizer as needed. The "sensitizer" which can be used in the present invention is not particularly limited, and can be arbitrarily selected from the sensitizer which is generally used in the positive resist composition 19 201028795. Specifically, a phenolic compound (Chemical Formula 8) R41 (HO), which is represented by the general formula (D-1), can be used.

(D - 1 [In the formula (D-1), R41 to R48 each independently represent a hydrogen atom, a halogen atom, a carbon number of 1 or more and 6 or less, and the carbon number is φ 1 or more and 6 or less. The alkoxy group or the cycloalkyl group; r49^" R疋 each independently represents a hydrogen atom or a group having a carbon number of 1 or more and 6 or less; Q represents a hydrogen atom, and the carbon number is 1 or more and 6 or less. The alkyl group and the carbon chain formed by bonding to R49 are a cyclic ring of 3 or more and 6 or less, or a residue represented by the chemical formula (D-2) shown below; w and s represent 1 or more and 3 The following integer; u is an integer representing 〇 or more and 3 or less; v is an integer representing 〇 or more and 3 or less;

〔化9〕

(D-2) [In the general formula (D-2), 'r52 and R53 are each independently represent a hydrogen atom, a dentate atom, an alkyl group having a carbon number of 1 or more and 6 or less, and a carbon number of 1 or more and 6 The following alkoxy group or cycloalkyl group; t is an integer representing 1 or more and 3 in *f. ]. The phenolic compound represented by the formula (D·1) as described above is 20 201028795 includes, for example, bis(4-hydroxy-2,3,5·trimethylphenyl)-2-hydroxyphenyl , 1,4-bis[1-(3,5-diamidino-4-hydroxyphenyl)isopropyl]benzene, 2.4-bis(3,5-dimercapto-4-hydroxyphenylindenyl) 6-nonylphenol, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2.5-dimethylphenyl)-2-hydroxyl Phenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[ 1 , 1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[丨_(3_methyl-4-hydroxyphenyl)isopropyl]_4_[l5l_bis(3_methyl_4•hydroxyl) • Phenyl)ethyl]benzene' 2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4-nonylphenol, 4,6-bis[1_(4-hydroxybenzene) Isopropyl]isophthalic acid, 4,6-bis(3,5-dimethoxyhydroxyphenylmethyl) galletol, 4,6-bis(3,5-dimethyl_4_ Hydroxyphenyl fluorenyl) gallic phenol, 2,6-bis(3-methyl-4,6-dihydroxyphenylmethyl)_4_A Phenol, 2,6_-bis (2,3,4-hydroxyphenylmethyl) _4 • methylphenol, Ul-bis (4-hydroxy-stupid-yl) cyclohexane, and the like. In addition, other 6_hydroxy_4a_(2, dehydroxydiphenyl)-9-1'-spirocyclohexyl-1,2,3,4,4&,9&-hexahydro-nest Yamaguchi, 6-hydroxyl-based 5-methyl-4a_(2,4-dihydroxymethylphenyl)-^^, spiro-hexyl-1,2,3,4,4&,93-hexahydro-nest Magnitude. These sensitizers may be used singly or in combination of two or more. Among them, it is preferably [1-(4-hydroxyphenyl)isopropyl]_4_[m (4-hydroxyphenyl) because of its superior high sensitivity and verticality of the space pattern. Combination of ethyl]benzene with bis(4-hydroxy-2,3,5-trimethylphenyl)_2-hydroxyphenyl f. Further, the 'sensitizer' is a phenolic compound represented by the formula (D-3) 21 201028795 as shown below. 〔化10〕

[In the general formula (D-3), R61 to R63 each independently represent a lower alkyl group, a cycloalkyl group, or a lower alkoxy group; q and oxime each independently represent 1 or more and 3 or less, and Preferably, it is an integer of 1 or more and 2 or less; 1. 〇, and ρ are integers each independently representing 0 or more and 3 or less. ]. Here, the lower alkyl group and the lower alkoxy group represented by R61 to R63 may be a straight bond or a branched chain, and preferably have a carbon number of 1 or more and 5 or less, more preferably a carbon number of 1 or more. And 3 or less. Further, the cycloalkyl group represented by R61 to R63 preferably has a carbon number of 5 or more and 7 or less. The compound represented by the formula (D-3), more specifically, φ is a compound represented by the following formula "D-4 to (D-8)" (Chemical Formula 11) 22 π years I month correction 201028795

Further, as the sensitizer, a "phenolic compound represented by the formula (D-9)" as shown below can be used. 〔化12〕

• (D-9) 23 201028795 [In the formula (D-9), R71 to R79 each independently represent a hydrogen atom, an alkyl group, a halogen atom, or a hydroxyl group, and at least one of the hydroxyl groups to R79 is a hydroxyl group. ; to R85 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group]. Wherein 'preferably at least one of R71 to R74 and at least one of R75 to R79 are a hydroxyl group. Further, the alkyl group represented by R71 to R79 may be linear or branched, and preferably has a carbon number of 丨 or more and 5 or less, more preferably 1 or more and 3 or less. And, with a ruler (10) to Μ5

The calcined group may be linear or branched, and preferably has a carbon number of 1 or more and 10 or less. R80 $85 et μ a , R ^ R ~ represents a carbon base. The number is 1 or more and 4 or less. The phenolic compound represented by the formula (d-9), as described above, more specifically, is exemplified by a compound. The following 7"General formula (D,) stands for [Chem. 13]

[In the formula 03,) towel, R86 and R87: . . . (D-1〇), f and g are integers representing i and above, and 3 π & each independently represents an integer of the alk, i and the county side* The S poly group from 疋1 or more and 2 or less represents an integer of 〇 above and below. ]. 24 201028795 wherein the alkyl group represented by ^ r»87 K and R may be linear or branched, i preferably has a carbon number of j or more and 5 or less, more preferably a carbon number of 1 or more. 3 or less. The phenolic compound represented by the formula (D-9) is not specifically mentioned above, and the compounds represented by the following formulas "Chemical Formulas (丨1) and (12)" are listed below. 〔化14〕

The amount of the sensitizer is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less based on the component (A) or the component (A') as described above. . [Other components] (Solvent) The positive resist composition of the present invention is preferably used in the form of a solution by dissolving each component as described above in a suitable solvent. Examples of such "solvents" include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. "diethylene glycol dialkyl ether" such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl race Lusu acetic acid 25 201028795 s 曰 曰 赛 赛 赛 赛 赛 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙"propylene glycol alkyl ether acetate" such as vinegar; "ketone" such as acetone, ethyl ketone, cyclohexanone or methyl amyl ketone; "aromatic" of toluene and hydrazine "Smoke"; "喔 喔 等 等 环 环 环 环 环 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经Ethyl oxyacetate, 2-hydroxy_3_methylbutyric acid, 3-methoxybutyl acetate, 3-methoxymethyl butyl sulfonate, ethyl acetate, ethyl acetate, acetic acid Vinegar, ethyl acetate "Ester" such as vinegar and acid I. These solvents may be used singly or in combination of two or more. Further, in order to obtain, for example, a film thickness of 3 or more by spin coating, it is preferred to use an amount of the solid content of the positive resist composition of 20% by mass or more and 65% by mass or less. Solvent (surfactant)

Further, the positive resist composition of the present invention may contain a surfactant in order to improve coatability, defoaming property, leveling property, and the like. The "surfactant" can be used, for example, BM-1000, BM-1100 (manufactured by BM-Chemie); MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAF AC F183 (Dainippon Ink and Chemicals, Inc.) Manufacturing); FLUORAD FC-135 'FLUORAD FC-170C > FLUORAD FC-430, FLUORAD FC-431 (Sumitomo 3M 26 201028795

Co., Ltd.), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (manufactured by Asahi Glass Co. Ltd.); SH-28PA Commercially available gas-based surfactants under the names SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.), etc. 'With respect to 100 parts by mass of the component (A) or (A'), it is preferably 5 parts by mass or less. φ (plasticizer) The positive photoresist composition of the present invention is further improved to avoid When a cracking resistanee such as crack is generated, an alkali-soluble acrylic resin can be used as a plasticizer. The alkali-soluble acrylic resin can be used as a plasticizer in a positive type. The alkali-soluble acrylic resin is more specifically, a structural unit derived from a poly-complex compound having an ether bond of 30% by mass or more and 90% by mass or less, and 2 parts by mass. The above and 50 parts by mass or less derived from the polymerization of a carboxyl group The structural unit of the substance. "Polymerizable compound having an ether bond" includes: (meth)acrylic acid 2-methoxyethyl ester, (meth)acrylic acid methoxy triethylene glycol ester, (methyl) Diethyl 3-methoxybutyl acrylate, ethyl methacrylate (meth) acrylate, phenoxy ethylene glycol (meth) acrylate, methoxy propylene glycol poly(decyl) acrylate A radical polymerizable compound 27, such as a (fluorenyl)acrylic acid derivative having a hydrazone bond and an ester bond, such as tetrahydrofurfuryl (meth) acrylate. Among them, it is preferred to use 2-methoxyethyl acrylate and methoxy triethylene glycol acetoacetate. These compounds may be used singly or in combination of two or more. The "polymerizable compound having a carboxyl group" includes "monocarboxylic acid" such as acrylic acid, methacrylic acid or crotonic acid; maleic acid (maleic acid), fumaric acid (fumaric acid), and y "Dicarboxylic acid" such as benic acid; 2-methylpropenyloxyethyl succinic acid, 2-methacryloxyethyl maleic acid, 2-methylpropenyloxyethyl A radically polymerizable compound such as phthalic acid or 2-methylpropane 1,3-alkenyloxyethylhexahydrophthalic acid having a carboxyl group and an ester bond. Among these, acrylic acid and mercaptoacrylic acid are preferably used. These compounds may be used singly or in combination of two or more. In the alkali-soluble acrylic resin component, the content of the "polymerizable compound having an ether bond" is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass or less. By setting the content to be 90% by mass or less, since the compatibility of the component (A) or the component (a,) does not deteriorate with respect to the solution, and the Benard cell does not occur during the prebaking (Bein cell) A pentagon to heptagon network pattern having unevenness on the surface of the coating film by gravity or a surface tension gradient or the like, a uniform photoresist film can be obtained, and if it is 30% by mass or more, when plating, No cracking occurred. In addition, the content of the "polymerizable compound having a carboxyl group" in the alkali-soluble acrylic resin component is preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less. By setting the content of the 28 201028795 to 2% by mass or more, the alkali solubility of the alkali-soluble acrylic resin component can be maintained at a high level, and sufficient developability can be obtained, and the peeling property is not lowered. The photoresist film is not reduced. Remains on the substrate. In addition, by setting it to 50% by mass or less, the residual film ratio after development can be maintained at a high level and a good plating resistance can be maintained. The mass average molecular weight of the soluble acrylic resin component is preferably 10,000 or more and 800,000 or less. More preferably, it is 3 Å or more and 500,000 or less. By setting it to 10 000 or more, the strength Φ of the photoresist film can be made variable enough, and the blister or crack of the profile at the time of plating is not caused. Further, by setting it to be 800,000 or less, the peeling property is not lowered. Further, in the determination of the soluble acrylic resin component, it is also possible to control the physical and chemical properties to an appropriate degree, and to contain a structural unit derived from another radically polymerizable compound. Here, the "other radical polymerizable compound" means a radical polymerizable compound other than the polymerizable compound as described above. ❹ These "radical polymerizable compounds" include "alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. j; "(hydroxy) hydroxyalkyl esters of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; phenyl (meth) acrylate, (methyl)) "(fluorenyl) aryl acrylates such as benzoquinone acrylate; "dicarboxylic acid diterpenes" such as diethyl maleate or dibutyl phthalate; styrene, alpha - "vinyl group-containing aromatic compound 29 201028795" such as mercaptostyrene; "vinyl group-containing aliphatic compound" such as vinyl acetate; "conjugated diene" such as dibutyl or isoprene "Polymerized compound containing nitrile group" such as acrylonitrile or mercapto acrylonitrile; "polymerizable compound containing gas" such as ethylene and vinylidene chloride; acrylamide and methacrylic acid A "polymerizable compound containing a guanamine bond" such as an amine. These compounds may be used singly or in combination of two or more. Among these compounds, n-butyl acrylate, thioglycolic acid benzyl acetate, methyl methacrylate and the like are particularly preferably used. The content of the other radically polymerizable compound which is present in the alkali-soluble acrylic resin component is preferably less than 50% by mass. /〇, preferably less than 40% by mass. For the "polymerization solvent" used in the synthesis of the alkali-soluble acrylic resin component, for example, "alcohol" such as ethanol or diethylene glycol; ethylene glycol-methyl ether, diethylene glycol monodecyl ether, and diethylene glycol can be used. "Polyol alcohol ethers" such as alcohol ethyl methyl ether; "polyol alkyl ether acetates" such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate vinegar; toluene' "Aromatic hydrocarbons" such as xylene ruthenium; "ketones J such as acetone and methyl isobutyl aryl; "esters" such as ethyl acetate and butyl acetate. Among these polymerizable solvents, particularly, polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ester acetates are preferably used. As the "polymerization catalyst" used in the synthesis of the soluble acrylic resin component, a general radical polymerization initiator can be used, for example, an "azo compound" such as 2,2, azobisisobutyronitrile or the like; An "organic peroxide" such as a base peroxide or a di-tertiary butyl peroxide. In the positive resist composition of the present invention, the amount of the soluble component of the soluble acrylic acid tree 30 201028795 is compared with respect to 100 parts by mass of the (A) wound or (A) component as described above. It is preferably 3 parts by mass or less and more preferably the parts by mass or less. [Modulation of positive-type photoresist composition] The positive-type photoresist composition of this month can be prepared by mixing and disturbing by a general method. In addition, screens, filters, etc. can be used further as needed. &lt;Formation Method of Photoresist Pattern&gt; The method of forming a photoresist pattern of Luben according to the present invention comprises the steps of: coating a positive-type photoresist composition of the present invention on a substrate to obtain a "coating step" of the photoresist film An "exposure step j for selectively exposing the photoresist film to actinic radiation; and a "development step" for developing the photoresist pattern after the exposure step. [Coating step] The positive-type resist composition of the present invention can be used, for example, when etching a substrate made of copper, or when forming a protective film for plating or a photoresist film for semiconductor manufacturing. In the "coating step" in the method of forming the photoresist pattern, the positive-type photoresist composition of the present invention is applied to a film thickness of 3 #m to 30/zm using a spinner or the like on the substrates, and Applying a pre-bake (PAB: Post Apply Bake) at a temperature of 80 C to 150 ° C for a period of 40 seconds to 600 seconds, preferably 60 seconds, depending on the thickness of the coating film or the intended use. Clock to 360 seconds to form a photoresist film. [Exposure step] For this photoresist film, for example, a low-pressure mercury lamp that emits a light source having a wavelength of 365 nm (i·ray) 31 201028795, 405 nm (h-ray), and 435 nm (g-ray), a high voltage Mercury lamp, ultra-high pressure mercury lamp, and selectively irradiated through the mask pattern of my desire, after application of post-exposure heating (PEB: Post Exposure Baking) at a temperature of 80 ° C to 150 ° C 40 seconds to 600 seconds, preferably 60 seconds to 360 seconds. In addition, the actinic radiation used for exposure can be used in addition to the low-pressure mercury lamp, the high-pressure mercury lamp, the g-ray of the ultra-high pressure mercury lamp, the h-ray, and the i-ray, and the ArF excimer laser can also be used. φ, KrF excimer laser, F2 excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (UV), electron beam (EB: electron beam), X-ray, soft X-ray ( Soft x-ray) is implemented by radiation. [Developing step] Next, the alkali developing solution of the tetramethylammonium hydroxide aqueous solution of, for example, 〇.i mass% or more and 10 mass%/〇 is used for the exposed photoresist film on 2〇t&gt;c# and below 30 C. It is developed at a temperature, then washed with pure water and washed with water and dried. Further, depending on the case, a baking treatment (post-baking) may be applied after the development treatment. By the steps as described above, a photoresist pattern faithful to the mask pattern can be obtained. According to the positive-type photoresist composition of the present invention and the method for forming a photoresist pattern using the same, since the positive-type photoresist composition contains a specific benzotris-based compound, the photoresist film is adhered to the substrate. The properties can be maintained so that a fine photoresist pattern can be formed, and at the same time, the amount of residue generated can be suppressed to a small amount after development of the photoresist film. 32 201028795 <<Example>> &lt;Preparation Example 1; Synthesis of alkali-soluble novolac resin A> Mixing m-cresol and p-cresol with m-cresol/p-cresol=6〇/4〇 (mass ratio), Further, formaldehyde (formalin) is added, and then an addition condensation is carried out by a conventional method using an oxalic acid catalyst to obtain a cresol novolac resin. This resin was subjected to a classification treatment to cut off the low molecular domain' to obtain an alkali-soluble novolac resin A having a mass average molecular weight of 2 Å. &lt;Example 1&gt; 69 parts by mass of "alkali-soluble novolac resin a" and 20 parts by mass of "sensitizer" 丨_[丨_(4-hydroxyphenyl)isopropyl]-4 - [1,1-bis(4-hydroxyphenyl)ethyl]benzene is a compound in which the 2 mol % hydrogen atom of all hydroxyl groups is substituted with 1,2-naphthoquinonediazide-5-sulfonyl 20 parts by mass of bis(4-hydroxyphenyl)cyclohexane as a "sensitizer" and 1 part by mass of a benzotriazole-based compound as a "adhesion enhancer" are represented by the following chemical formula ( The compound _ represented by C-1) was dissolved in propylene glycol monoethyl ether acetate and adjusted to have a solid concentration of 43% by mass to prepare a positive resist composition. 〔化15〕

• (C-1) &lt;Example 2 &gt; 33 201028795 In addition to the benzotristrin compound will be as above;

The compound represented by the formula (CM) is substituted, and the compound represented by the formula (C-2) shown by τ 7 is used, and the others are prepared in the same manner as in the case of Example 1. Photoresist composition. 〔化16〕

(C-2) &lt;Comparative Example 1 &gt; Except that the benzotrisal compound is substituted with the compound represented by the above formula (C), and the other is the use of mercaptobenzene = saliva. The positive photoresist composition was prepared in the same manner as in Example i. &lt;Comparative Example 2 &gt; In addition to the adhesion improving agent, it is a benzotriazole-based compound as above

The compound represented by the chemical &lt;(CM) was replaced, and the positive resist composition was prepared in the same manner as in Example i except that pyridine alcohol was used. &lt;Comparative Example 3 &gt; The positive resist composition was prepared in the same manner as in the example except that the compound represented by the above formula (C-1) was not added to the benzotriazole-based compound. . &lt;Performance Evaluation&gt; [Presence or absence of residue] On a substrate obtained by sputtering copper on a stone wafer at a thickness of 500 nm 34 201028795 'Coating Example 1, 2, and Comparative Examples 1 to 3 The photoresist composition was dried and dried on a hot plate at 110 ° C for 240 seconds to obtain a photoresist film having a film thickness of 1 〇 / / m. Next, the film was placed under the mask of a light shading pattern, and a reduction projection exposure apparatus "NSR-2005il0D" (trade name, manufactured by Nikon Corp.) was used. , NA = 0.50) 'Exposure is performed up to an exposure amount up to 1.2 times the minimum exposure amount (ΕΤΗ) that can be developed. In the developing operation, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developing solution for the photoresist film, and after maintaining for 60 seconds, the developer was removed by the rotation of the rotary machine. After the development operation was repeated three times, it was washed with water for 30 seconds and dried. Thereafter, the photoresist-substrate interface of the 20/zm spatial pattern obtained by observation was observed by a scanning electron microscope (SEM), and it was confirmed that the photoresist residue (scum) was observed around the pattern. If you cannot confirm, you will see it as "〇". [Adhesion evaluation 1 (adhesiveness during development)] The positive light of Example 丨, 2, and Comparative Example 丨 was applied to a substrate obtained by sputtering copper on a ruthenium wafer at a thickness of 500 nm. The composition was blocked and dried on a hot plate at 110 C for 240 seconds to obtain a photoresist film having a film thickness of m from m. Next, the film is covered with a mask for drawing a predetermined light-shielding pattern, and the projection exposure apparatus "NSR_2005il〇D" (trade name, manufactured by Nikon Corporation, 2010 2010 795, NA-0.50) is used until the lowest exposure is developable. The exposure amount from 1.0 times to 1.4 times the amount (etH) is exposed. In the developing operation, a 2.38 mass% tetrahydric hydroxide tetrahydroxide (TMAH) aqueous solution was used as the developing solution for the photoresist film, and after maintaining for 6 seconds, the developer was removed by the rotation of the rotary machine. This development operation was repeated three times, and then washed with water for 30 seconds and dried. Thereafter, the photoresist pattern was observed by an optical microscope, and the repeating pattern of the line/space (hne-and-space) and dot (dot) of 1 〇//m was only 1.0 times the size of the 密. Rx" is still "△" until it is still close to 12 times, and is considered "〇" until it is still "1". [Adhesion evaluation 2 (measurement of side etching amount)] On a substrate obtained by sputtering copper on a rare wafer at a thickness of 500 nm, a positive photoresist was applied in the same manner as in [Adhesion evaluation 1]. After the composition and the exposure and development of the photoresist film, the "vaporized iron (III) solution" (trade name, pure chemical company) (trade name) is impregnated at 23 ° C and is 45 &lt;&gt; After 5 seconds from Jimsei Chemical Co., Ltd., the etching length of the copper at the bottom of the photoresist was measured using a scanning electron microscope (SEM). If the erosion length is 5#m or more, it is regarded as “χ”, and if it is 30m or more and less than 5, m is regarded as “△”, and if it is less than 3 #m, it is regarded as “〇 [solubility test] in 300 ml. In the beaker, 65 parts by mass of the alkali-soluble novolac tree 36 201028795 fat A and 5 parts by mass of the adhesion enhancer were added to the composition of Example 1 λ 2 and Comparative Examples 1 and 2, and propylene glycol-acid was added. The vinegar is added to a solid concentration of 43 ft%, after::, and mixed for 1 hour. The person who is completely dissolved by visual inspection is regarded as "X". The results are as shown in Table 1.

As in Table 1*, in Examples 1 and 2 in which the benzotriazine compound of the present invention was used, the production of money was not included in the benzotriazole system represented by the above formula (1). Comparative Example 1 of the carboxybenzotriazole of the compound was suppressed and suppressed. Further, in Examples 1 and 2, the adhesion between the photoresist film and the substrate was better than Comparative Examples 2 and 3 in which the benzotriazole-based compound was not used, and the generation of residue was also less. . [Industrial Applicability] As described above, the positive resist composition of the present invention can maintain the adhesion between the photoresist film and the substrate, and can suppress the amount of residue generated to a small amount. 37

Claims (1)

201028795 VII. Patent application scope: 1. A positive-type photoresist composition comprising: (A) a soluble solvent: resin, (8) sensitizer, * (C) stupid triazole compound, and the aforementioned benzo The tri(tetra) compound is a compound represented by the following formula (1): [Chemical 1] • (1) [In the general formula (1), W represents an alkyl group having a carbon number of 1 or more and less, a hydroxyl group, a carboxyl group, a hydrogen atom, or — C〇〇R, (R, is the carbon number is 1 or more and 5 or less alkyl groups; R1 and R3 are each independently represent a hydrogen atom, an alkyl group having 1 or more and 6 or less carbon atoms, or a hydroxy group having 1 or more and 6 or less carbon atoms. At least one of the ruler 1 and the han 2 is a hydroxyalkyl group having a carbon number of 1 or more and 6 or less. 38 1 — A positive-type photoresist composition comprising: (A′) a phenolic hydroxyl group having at least a portion of a halogen atom substituted by a 1,2-naphthoquinonediazidesulfonyl group a novolak resin, and (C) a benzotriazole-based compound, and 2 the aforementioned benzotriazole-based compound is a compound represented by the following formula (1): [Chemical 2] π年·月修正201028795 [In the formula (1), R1 represents an alkyl group having a carbon number of 1 or more and 10 or less, a hydroxyl group, a carboxyl group, a hydrogen atom, or a COOR' (R' is an alkyl group having a carbon number of 1 or more and 5 or less. R2 and R3 are each independently an alkyl group having a hydrogen number of 1 or more and 6 or less, or a base having a carbon number of 1 or more and 6 underarm, but selected from R2 and R3. At least one is a hydroxyalkyl group having a carbon number of 1 or more and 6 or less. 3. The positive-type photoresist composition according to claim 2, further comprising (B) a sensitizer. The positive-type photoresist composition according to claim 1 or 2, wherein R2 and R3 are a hydroxy group having a carbon number of 1 or more and 6 or less. 5. The positive-type photoresist composition according to claim 4, wherein R2 and R3 are 2-hydroxyethyl groups. 6. Please ask for the scope of patents! Or a positive-type photoresist composition according to item 2, wherein R1 is an alkyl group having a post number of 1 or more and 3 or less. A method for forming a photoresist pattern includes the following steps: 39 201028795 coating a positive photoresist composition as described in claim 1 or 2 on a substrate to obtain a coating step of the photoresist film; An exposure step of exposing the photoresist film to actinic radiation; and developing after the foregoing exposure step to obtain a development step of the photoresist pattern. 40 201028795 IV. Designated representative map: (1) The representative representative of the case is: None. (2) The symbolic representation of the symbol of the representative figure is simple: none. Φ 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: