TWI296741B - Chemically amplified positive photoresist composition - Google Patents

Description

1296741 (1) EMBODIMENT DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a chemically enhanced positive-type photoresist composition. The present invention is based on the patent application No. 2004-1 1 5 3 2 8 filed on Apr. 9, 2004, the priority of which is hereby incorporated by reference. % [Prior Art] In recent years, in the field of manufacturing semiconductor elements, liquid crystal display devices (LCDs), printed circuit boards, bumps, magnetic heads, etc., alkali-soluble resins and quinonediazide are generally used. a compound of the base compound ('PAC) as a main component of the g~i line photoresist composition, or an i-line containing a acid dissociable group w' compound (resin) and a photoacid generator (PAG) as a main component, KrF A chemically amplified photoresist composition for use with, ArF or electron wires. The known chemically-enhanced photoresist composition is as described in the following Patent Documents 1 to 4, and the like. In the patent document 1 (Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Things and so on. An alkali-soluble resin having a hydroxyl group in a branched chain such as a novolac resin, and a specific one, is described in the patent document 2 (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. A chemically amplified positive photoresist material such as a crosslinking agent or an acid generator. Patent Document 4 (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. 2002-5 2 95 5 2) contains -5- (2) (2)

In the "Implantation Process", it is necessary to embed an impurity of % degree. In this implantation process, the vacuum is extremely high, but the heat generated by the impregnation is generated, and the photoresist pattern is formed, which causes the shape of the photoresist pattern to change, and some components in the pattern. Vaporization to reduce the degree of vacuum in the treatment chamber 1296741 The polymer which partially crosslinks the hydroxyl group-containing polymer and the polyethylene group in the presence of an acid catalyst, and the composition of the PAG. However, with the advancement of technology in various fields, there is a need for the heat resistance of the photoresist composition in combination with its use. For example, it is expected that a high-performance LCD of a drive circuit, a DAC (digital-to-analog converter), a picture signal, a video controller, a RAM, and the like, and a high-performance LCD of a display unit "system LCD" on one glass substrate are expected. One generation; Semiconductor FPD World 200 1. 9? pp. 5 0-6 7 ) ° In the TFT of the above system LCD (thin film transistor), the low temperature polysilicon produced by the low temperature process below °C is far less than Lower resistance and higher mobility are preferred. When a TFT is produced by using a low-temperature polysilicon, after forming a polycrystalline germanium film in a glass substrate process, embedding P or B in the low-temperature polyphenolic phenol resin is suitable as a tree of inexpensive and excellent heat resistance, but one of hydrogen atoms in the hydroxyl group of the phenol resin. The resin component obtained by partial protection by an acid-suppressing group is used as a resin component of a chemically-enhanced positive-type photoresist composition because of its extremely poor heat resistance. The ether reaction is often used to form the processor at the same time, ie > LCD (F is a 60-inch crystal cookware in a low-temperature tantalum film, which has a very high concentration to heat the substrate or make the photoresist, etc. The problem is that it is difficult to make a dissolving solution. (3) 1296741 In order to solve the above problems, for example, a resin component can be polymerized*' or a phenolic resin or a fat synthesized by using a high-volume-density aromatic hydroxy compound. However, in any of the methods, the alkali solubility of the resin component tends to be deteriorated, and thus the resolution of the photoresist composition is deteriorated. In order to solve the above problems, it is currently before the intrusion process. First, a heat treatment step generally referred to as "pre-firing" is carried out, which is carried out at a temperature close to the heating temperature at the time of implantation, for example, at a high temperature of 1 at 60 ° C. Therefore, It is still necessary to have properties such as heat resistance which does not change the shape of the photoresist pattern in the above heat treatment. The present invention has been made in view of the above circumstances to provide a phenol resin. The resulting fat composition has excellent heat resistance of a chemical amplifying type positive resist composition for the purpose of the invention. SUMMARY OF THE INVENTION The present invention is to employ the following configuration to achieve the foregoing object.

That is, a chemically-enhanced positive-type photoresist composition is provided which contains (A) a resin component, (C) a compound which generates an acid component by radiation irradiation, an organic solvent, and has a component (C) via the foregoing (C) A chemically amplified positive-type photoresist composition capable of increasing the solubility of an aqueous alkali solution by the action of an acid component, wherein the component (A) contains an aromatic hydroxy compound and at least contains formaldehyde. In the phenol resin (a 1 ) obtained by condensation reaction of an aldehyde substituted with a hydroxy-substituted aromatic aldehyde, one part of the total phenolic hydroxyl group is characterized by a poorly soluble or insoluble resin component protected by an acid dissociable dissolution inhibiting group. Chemistry (4) 1296741 隹 Enhanced positive photoresist composition. The component (A) is contained in a poorly soluble or insoluble resin which is contained in the phenolic resin (al) and is partially protected by an acid dissociable dissolution inhibiting group. The resin component obtained by the molecular weight treatment is preferred. Further, the component (A) contains a phenolic resin containing at least a percentage of the aromatic hydroxy compound' which is obtained by a condensation reaction of at least a awake and a trans-substituted aromatic oxime, and is subjected to removal of the low molecular weight body, respectively. It is preferred that a part of the total phenolic hydroxyl group of the acid aldehyde tree (a2) is poorly soluble or insoluble in the base obtained by protecting the acid dissociable dissolution inhibiting group. In a preferred embodiment (A), the component (A) is a poorly soluble or insoluble resin component of the component (A). The phenolic resin (a1) can be synthesized by addition reaction with a compound corresponding to the acid dissociative dissolution inhibiting group. . The phenol resin (a 1 ) can be obtained by subjecting an aromatic hydroxy compound and an aldehyde to a condensation reaction. The aromatic hydroxy compound used in the synthesis of the phenolic resin (a1), such as phenol; cresol such as ηι_cresol, p-cresol or hydrazine-cresol; 2,3-xylenol, 2,5- Xylenols such as xylenol, 3,5-xylenol, 3,4-xylenol; ηι·, ethylphenol, ρ·ethylphenol, 〇·ethylphenol, 2,3,5- Trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methyl Alkylphenols, 2-tert-butyl-5-methylphenol and other alkylphenols; (5) 1296741 p-methoxyphenol, m-methoxyphenol, p-ethoxy oxime, m-ethoxylate Alkoxyphenols such as phenyl, P-propoxy phenol, m-propoxy phenol, oxime-isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2 -Isopropenylphenols such as ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and coke Polyphenols such as phenols. They may be used singly or in combination of two or more. Among them, m- and p-cresol are preferred.

The aforementioned aldehyde used in the synthesis of the phenol resin (a 1 ) contains at least a formaldehyde and a hydroxy-substituted aromatic aldehyde. The hydroxy-substituted aromatic aldehyde is preferably, for example, a hydroxybenzaldehyde represented by the following formula (I), and particularly preferably a compound wherein η is 1 or 2 in the formula. Specifically, for example, hydroxybenzaldehyde (salicylate), hydrazine-hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, and the like. They may be used singly or in combination of two or more.

(1) (where η is an integer from 1 to 3). When the aldehyde used in the synthesis of the phenol resin (a1) is used as an essential component by using a hydroxy group instead of other aromatic aldehydes, it is easier to polymerize than the hydroxy-substituted aromatic aldehyde having a poor reactivity. In the aldehyde, an aldehyde other than the aromatic aldehyde may be substituted with the above-mentioned formaldehyde and a hydroxy group. For example, formaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanal, furfural, furyl acrolein, and the like can be used. It is also possible to use two or more types. -9- (6) 1296741 The condensation reaction product of the above aromatic hydroxy compound with an aldehyde can be obtained by a known method in the presence of an acidic catalyst. As the acidic catalyst to be used at this time, for example, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid or the like can be used. The amount of the aldehyde used is preferably from about 50 to about 1 mole per mole of the aromatic hydroxy compound, more preferably from about 60 to 80 mole %.

When the amount of the hydroxy-substituted aromatic aldehyde is too small, sufficient effect of addition is not obtained, and when it is too large, the polymer is not easily formed, and sufficient effects are not obtained, and the adverse effect of excessive raw material cost is also caused. Therefore, it is preferable to add about 10 to 50 mol%, more preferably about 20 to 35 mol%, to the total aldehyde amount. Further, when the amount of formaldehyde used is too small, the molecular weight is not easily increased. When the amount is too large, there is a concern that the alkali dissolution rate decreases as the molecular weight increases. Therefore, it is preferable to use a total aldehyde amount of about 50 to 90 mol%. Good is about 65 to 8 〇%. In the aldehyde to be used, the ratio of the total amount of formaldehyde to the hydroxy-substituted aromatic aldehyde is preferably 80 mol% or more, and more preferably 100 mol%. When the mass average molecular weight (Mw) of the phenol resin (al) is too small, the coating property is inferior and tends to be deteriorated. When the phenolic resin (al) is too large, the resolution tends to deteriorate. The Mw of the phenol resin (al) is preferably in the range of from 1 Å to 1,000 00000, more preferably from 2,000 to 50,000, most preferably from 3,000 to 30,000. In the present embodiment, at least -10 (7) 1296741 1 of the total phenolic hydroxyl groups in the phenol resin (a 1 ) is a base which is decomposed and converted into an alkali solubility by an acid catalyst reaction, that is, a so-called acid dissociable dissolution. Those who are protected by the inhibitory group can be protected by the insoluble or insoluble nature of the base.

The acid dissociable dissolution inhibiting group may be any one which can be dissociated by the acid produced by the component (C) described later, for example, 1 · ethoxymethyl, 1-ethoxyethyl, propoxymethyl, 1- Alkoxyethyl, 1-n-butoxymethyl, iso-butoxymethyl, Ι-tert-butoxymethyl, etc.; t-butoxycarbonyl, t- Alkoxycarbonylalkyl group such as butoxycarbonylmethyl, t-butoxycarbonylethyl; tetrahydrofuranyl; tetrahydropyranyl; linear or branched acetal; cyclic acetal; A trialkylalkylene group such as a methyl decyl group, a triethyl decyl group or a triphenyl decyl group. Further, an ethylvinyl group (ethoxyethyl group) represented by the following chemical formula (Π -1 ) and a t-butoxycarbonyl group represented by the following chemical formula (Π-2) are used to obtain light having excellent resolution. It is preferable to block the composition, and it is more preferable to use an ethyl vinyl group. —C2H5 ·*·(!!-1) ch3 (H-2) -C-0-C(CH3)3 The total phenolic hydroxyl group in the phenolic resin (a 1 ) is protected by an acid dissociable dissolution inhibitory group. The ratio of the phenolic hydroxyl group (protection ratio) is preferably from about 1 50 to about 50 mol%. -11 - 1296741 (δ) (c) The component (c) is not particularly limited. It can be used as a photoacid generator which has been conventionally used as a chemically-enhanced positive photoresist material. For example, sulfonyldiazo can be used. A methane acid generator, a key salt acid generator, an oxime sulfonate acid generator, and the like. The component (C), for example, the following compounds have a high acid production efficiency for i-line exposure, and are therefore preferred. It is represented by the following formulas (III) and (IV), % R1',

A R3’ · · (Π) R5

ο II C=CC=N-0—S-R3/ \ / ιι R2 A 0 αν) (where m' is 〇 or 1; X is 1 or 2; R! is 6 or more When the C12 alkyl group may be substituted with a phenyl group, a heteroaryl group or the like 'or m' is 0, it may be a C2 to C6 courtyard oxygen ore group, a phenoxy amine group, a CN group or the like; and Rl' is a 匸2 to 'c12 extension. Alkyl, etc.; R2 has the same meaning as R; R3 is C! to c18 alkyl; etc.; R3' has the same meaning as R3 when x = 1 'C2 to C when 2 = 2 Phenyl or the like; R4 and R5 are independently a compound of a hydrogen atom 'halogen, -12-(9) 1296741 <^ to C6, and the like; A is S, 0, NR6, etc.; 116 is an equivalent compound (USP 6004724). Specifically, the sulfur-containing sulfonate or the like is represented by (V). C3H7 / 0 /

A hydrogen atom or a phenyl group, for example, the following formula "(V) CH3 or the following formula (v I ) Ν R6〇

CH = CH Λ CC13 Ν=^ R70 CC13 (wherein chloromethyl VII )

R6 and R7 are each an alkyl group having 1 to 3 carbon atoms), or a compound of the compound (VI (VI) and a double (III) and a formula (CC13 CC13 (wherein Z is 4- Alkoxyphenyl group, etc. shown as a double (three compound combination obtained (Special Kaiping 6-2 8 96 1 4 public 2 • " (W) chloromethyl) triterpenes, special Kaiping 7--13- (10) 1296741 1 3 44 1 2).

The three-till compound (VI) is specifically, for example, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3, 5- Triterpenoid, 2-[2-(3-methoxy-4-ethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2- [2-(3-Methoxy-4-propoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3 -ethoxy-4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-di-B Oxyphenyl)vinyl]·4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3-ethoxy-4-propoxyphenyl) Vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2·[2-(3-propoxy-4-methoxyphenyl)vinyl]-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-propoxy-4-ethoxyphenyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-three tillage, 2-[2-(3,4-dipropyloxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1, 3,5-three tillage and so on. The above three tillage compounds may be used singly or in combination of two or more. Further, the above-mentioned three-till compound (VII) which can be used in combination with the above-mentioned three-till compound (VI) is, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-three tillage, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-propoxyphenyl)- 4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5 -Tri-trap, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-trin, 2-(4-ethoxynaphthyl)-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-propoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5- Three tillage, 2-(4-butoxynaphthyl)-4,6-bis(trichloromethyl)- -14- (11) 1296741 1,3,5-three tillage, 2-(4-methoxy -6-carboxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triphthyl, 2-(4-methoxy-6-hydroxynaphthyl)-4,6 - bis(tri-chloromethyl)-1,3,5-trimorphine, 2·[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)_1,3, 5 - Three tillage, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2- (5-ethyl-2-furan) )vinyl]-4,6-bis(trichloromethyl)-1,3,5 tri-farming, 2-[2-(5-propyl-2-furyl)vinyl]-4,6- Bis(trichloroindenyl)-1,3,5-trimethyl, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl) -1,3,5-three tillage, 2-[2-(3-methoxy-5-ethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3, 5-trin, 2-[2-(3-methoxy-5-propoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-trian, 2-[2-(3-ethoxy-5-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-trimorphine, 2-[2- (3,5-Diethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-ethoxy-5 -propoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-% propoxy-5-methoxy Phenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-trin, 2-[2-(3-propoxy-5-ethoxyphenyl)vinyl ]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3,5-dipropoxyphenyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-three tillage, 2-(3,4-methyldioxyphenyl) -4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3,4-extended methyldioxyphenyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-~ three tillage. The three tillage compounds may be used singly or in combination of two or more. Also, for example, the following formula (VIII) -15- (12) 1296741

\ 0 \|!^r (10) S /π 〇 (wherein Ar is a substituted or unsubstituted phenyl or naphthyl group; R is an alkyl group of C! to C9; η is an integer of 2 or 3) Compound. These compounds may be used singly or in combination of two or more kinds. Among the above-exemplified compounds, in particular, the compound represented by the above formula (V) and the compound represented by the following formula (IX) have an excellent acid generating efficiency for i-rays, and therefore are suitably used.

In the present embodiment, one type of the component (C) may be used alone or two or more types may be used in combination. The amount of the component (C) to be added is preferably from 1 to 30 parts by mass per 100 parts by mass of the component (A), and more preferably from 1 to 20 parts by mass. (D) Component The chemically-enhanced positive resist composition of the present embodiment is preferably a basic compound (preferably an amine) to which (D) is added for the purpose of improving storage stability. -16- (13) 1296741 The compound is not particularly limited as long as it has compatibility with the photoresist composition, and for example, a compound described in JP-A-9-600 No. 1 can be used. In particular, when a basic compound (d 1 ) having a higher bulk density represented by the following formula (X) is added, the amount of the acid component of the by-product in the resist composition during storage can be effectively suppressed, and the photoresist can be improved. Long-term storage stability of the composition.

N-Y ."(X)

I

In the formula (X), one or more of X, Y, and Z (preferably two or more, more preferably three) are represented by the following (1) to (4), and (1) carbon number of 4 or more The alkyl group, (2) a cycloalkyl group having 3 or more carbon atoms, a (3) phenyl group or a (4) aralkyl group; preferably a selected group.

Further, in addition to the above (1) to (4), X, oxime and oxime may be, for example, (1') an alkyl group having 3 or less carbon atoms, or a (2') hydrogen atom, or a selected one or atom. Χ, Υ, Ζ may be the same or different from each other, and if two or more of Χ, Υ, Ζ are selected from the above (1) to (4), the above-mentioned groups are more similar to each other. It is better to stabilize the effect. (1) Alkyl group having 4 or more carbon atoms In the case of the above (1), when the carbon number is less than 4, it is difficult to increase the storage stability of -17-(14) 1296741. The carbon number is preferably 5 or more, particularly preferably 8 or more. The upper limit is not limited, but it is generally 20 or less, more preferably 15 or less, from the viewpoint of confirming storage stability or being commercially available. Further, when the temperature exceeds 20, the alkali strength is lowered, so that the effect of storage stability is lowered. The alkyl group may be linear or branched. Specifically, ’' is preferably η-fluorenyl, 11-octyl, n-pentyl or the like.

(2) A ring having a carbon number of 3 or more is preferable because the cycloalkyl group having a carbon number of 4 to 8 is easily commercially available and can improve storage stability and the like. Special 'is a cyclohexyl group with a carbon number of 6 being more preferred. (4) Aralkylalkyl Aralkyl group, for example, represented by the formula -R ' - P ( R ' is an alkylene group, and P is an aromatic hydrocarbon group. P is, for example, a phenyl group or a naphthyl group, and a phenyl group is preferred. The carbon number of R' is preferably 1 or more, more preferably 1 to 3. An aralkyl group such as a benzyl group, a phenethyl group or the like is preferred. Further, among X, Y, and Z, those not belonging to the above (1) to (4), and % are the groups or atoms selected in the above (1') and (2'). ^ ( 1 ') may be linear or branched. In particular, methyl or ethyl groups are preferred. ' (d 1 ) component, preferably composed of tertiary amines, X, γ, Ζ -18- (15) 1296741, not belonging to the above (1) to (4), to (1 ' The selected one is better. For example, specifically, it is a tri-n-decylamine, a methyl-di-n-octylamine, a tri-n-pentylamine, an N,N-dicyclohexylmethylamine, a tribenzylamine or the like. Among them, one or more selected from the group consisting of di-n-decylamine, methyl-mono-n-semiylamine and tris-pentylamine are preferred, and in particular, tris-n-decylamine is further good. In the present embodiment, the component (D) may be used singly or in combination of two or more.

The amount of the component (D) to be added is preferably 丨1 to 5.0 parts by mass based on 00 parts by mass of the resin solid component, and more preferably 0.1 to 10,000 parts by mass. Organic solvent The organic solvent in the resist composition of the present embodiment is not particularly limited as long as it is a solvent used for the chemically amplified positive resist composition. For example, it may be an ester solvent such as propylene glycol monoalkyl ether acetate (for example, propylene glycol monomethyl φ ether acetate (PGMEA), or a lactate (for example, ethyl lactate), acetone, methyl ethyl ketone. , ketones such as cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl Polyols such as ethers or monophenyl ethers and derivatives thereof; cyclic ethers such as dioxane; and non-ester solvents. Further, the ester is a solvent such as a reaction product of an organic carboxylic acid and an alcohol, which contains an organic acid of a free acid. Therefore, it is preferable to select the photoresist composition of the above (D) component or the photoresist composition which does not add the storage stabilizer described later, and it is preferable to select from the above-mentioned non-ester solvent containing no free acid, particularly a ketone. The class (ketone solvent -19-(16) 1296741) is preferred. Further, 2-heptanone is more preferable from the viewpoints of coating property and solubility of (C) component. And an 'ester solvent or a non-ester solvent, which produces by-products such as acid when decomposed for a long period of time, so it can be suppressed in the presence of the above component (D) or in the presence of a storage stabilizer as described later. The decomposition reaction. In particular, it is preferable to use an ester solvent in the presence of a storage stabilizer, particularly in the case of an ester solvent, and it is more preferable to use PGMEA. Further, when the acid component of the by-product of the decomposition reaction is, for example, 2-heptanone, it is confirmed that formic acid, acetic acid, propionic acid or the like is generated. The organic solvent may be used alone or in combination of two or more. • Other components In the chemically amplified positive resist composition of the present embodiment, it is preferred to further add the following storage stabilizer if necessary.

The storage stabilizer is not particularly limited as long as it has a decomposition reaction capable of suppressing the organic solvent. For example, an oxidation preventive agent or the like disclosed in Japanese Laid-Open Patent Publication No. SHO-58-8494. Oxidation preventive agents are generally known, for example, as phenolic compounds and amine compounds, and phenolic compounds are preferred as 2,6-di(tert-butyl)-P-cresol and derivatives thereof, which are effective for preventing esters. It is preferred that the solvent and the ketone solvent are deteriorated, and it is easy to obtain a commercial price and an excellent storage stability effect. In particular, it has an excellent effect of preventing deterioration of propylene glycol monoalkyl ether acetate, 2-heptanone or the like. Further, in the range of -20-(17) 1296741, which is not detrimental to the object of the present invention, the photoresist composition of the present embodiment may further contain a compatible additive, for example, a modified-good photoresist film property. Resins, plasticizers, surfactants, pigments for developing and developing conditions, sensitizers for sensitizing effects, dyes for anti-halation, and adhesion promoters. • Method for Producing Positive-Type Photoresist Composition The positive-type photoresist composition of the present embodiment can be obtained by dissolving (A) component, % (C) component, and other components added as necessary in an organic solvent. Manufacturing. The amount of the organic component used may be dissolved by (A) component, (C) component, and other components added as necessary to form a uniform positive photoresist group _· It is preferably used in such a manner that the solid content concentration is adjusted to 1 Å to 50% by mass, more preferably 20 to 35% by mass. Further, the solid component of the positive resist composition is equivalent to the total amount of the component (A), the component (C), and other components added as necessary.

• Method of Forming Photoresist Pattern The following is a preferred example of a method for forming a photoresist pattern using the photoresist composition of the present embodiment. First, the component (A) and the component (C), and various components added as necessary, are dissolved in a solvent, and applied to a substrate using a spin coater or the like to form a coating film. The substrate may be a tantalum substrate, a glass substrate or the like, and may be appropriately selected in accordance with the use. Next, the substrate on which the coating film was formed was subjected to heat treatment (pre-baking -21 - (18) 1296741) to remove the residual solvent to form a photoresist film. In the method of pre-baking, when the glass substrate is used for the substrate, it is preferable to have a gap between the hot platen and the substrate. In the present embodiment, the heating condition of the pre-firing is preferably set to about 80 to 150 ° C and about 60 to 300 seconds. Next, the photoresist film is selectively exposed through the photomask. The light source used therein can be appropriately selected according to the type of (C) component. For example, when using PAG for i-ray, the light source preferably uses i-ray (3 6 5 n m). Next, the photoresist film after selective exposure is subjected to heat treatment (post-burning). The method of P EB is, for example, a method in which a hot plate and a substrate have a short gap between the substrates, and a direct firing without a gap, and when the substrate is used, the glass substrate is prevented from being warped by the substrate. In the case of the PEB diffusion effect, it is preferred to perform the direct firing after the near-boiled culture. In the present embodiment, the heating condition of the PEB is preferably set to about 80 to 150 ° C and about 60 to 300 seconds. With respect to the film after the PEB, a developing solution, for example, an aqueous alkali solution such as 1 to 1% by mass of a tetramethylammonium hydroxide aqueous solution, is applied to the developing treatment to dissolve and remove the exposed portion while forming light on the substrate. Resistance pattern. Next, the developer remaining on the surface of the resist pattern is washed with pure water or the like to form a photoresist pattern. The inventors of the present invention have conducted detailed investigations on the heat resistance of the chemically-enhanced positive-type photoresist composition, and have found that, in particular, the phenolic hydroxy-22-(19) 1296741 of an alkali-soluble resin and an acid dissociable dissolution inhibiting group are obtained. When the reaction is carried out, the heat resistance is remarkably lowered as the phenolic base group is reduced. On the other hand, when the alkali-soluble resin polymer is quantitatively quantified or introduced into a structural unit having a high bulk density to improve the heat resistance, the photoresist composition tends to cause a decrease in solubility to the alkali developer. Doubts such as deterioration in resolution. Further, in the present embodiment, in particular, the alkali-soluble resin constituting the component (A) is obtained by a condensation reaction of an aromatic hydroxy compound with an aldehyde containing formaldehyde and a hydroxyl group to obtain an aromatic aldehyde. At the same time, the heat resistance of the positive resist composition can be improved. It is presumed that the phenolic resin (a1) has a benzene ring density as a result of containing a hydroxy-substituted aromatic aldehyde in the condensing agent, and as a result, the heat resistance of the phenolic resin (al) which causes steric hindrance can be improved. Further, by using the hydroxy group instead of the aromatic aldehyde, the resolution can be improved. It is presumed that when an aromatic aldehyde having a phenolic hydroxyl group (hydroxy-substituted aromatic aldehyde) is used in the condensing agent, the phenolic hydroxyl group present in the phenol resin (a1) can be increased, and the phenolic resin (a1) itself can be increased. The base is soluble. Further, since the positive resist composition of the present embodiment has a mechanism of chemically enhanced type, the contrast between the unexposed portion and the exposed portion is extremely strong, so that good resolution and sensitivity can be obtained. Further, since the phenol resin has advantages such as being inexpensive and easily obtained, it is possible to provide a positive-type resist composition which is inexpensive and has excellent heat resistance. Further, the heat resistance of the positive-type resist composition means an effect of preventing deformation of the resist pattern during high-temperature heat treatment, and an effect of preventing a change in the size of the resist pattern. -23- (20) 1296741 [Second embodiment] The present embodiment differs from the first embodiment in that, when the component (A) is prepared, the phenol resin (a 1 ) and the corresponding acid dissociable solution are dissolved. In the reaction product (base poorly soluble or insoluble resin) obtained by the reaction of the compound of the inhibiting group, the resin component obtained by the treatment for removing the low molecular weight body is used as the component (A).

The low molecular weight body in the present specification includes, for example, a residual monomer, a dimer having a 2-molecular bond, a trimer having a 3 molecule bond, and the like (monomer and 2 to 3 nucleus, etc.). For the treatment method of the low molecular weight body, for example, the phenol resin protected by the acid dissociable dissolution inhibiting group can be subjected to a purification method such as an ion exchange resin. According to this method, the acid component or the metal component can be removed while removing the low molecular weight body. Further, a method in which a phenol resin dissolved in a good solvent is added to a poor solvent to be separately precipitated, and a low molecular weight body is removed by taking out a precipitate is obtained, and the yield of the respective removal treatment of the low molecular weight body is 50 to A range of 95% by mass is preferred. When the amount is less than 50% by mass, the solubility in the aqueous alkali solution cannot be sufficiently increased by the action of the acid component generated by the component (c) described later. As a result, the dissolution rate between the low-exposure portion and the unexposed portion is made worse, and the resolution is lowered. Further, when it exceeds 95% by mass, even if the respective removal treatments are carried out, an excellent effect cannot be obtained. Further, the content of the low molecular weight -24-(21) 1296741 having a M w of 500 or less is 15% or less, preferably 12% or less on the GPC chart. When it is less than 15%, the effect of improving the heat resistance of the resist pattern can be achieved, and the effect of lowering the sublimation produced by heating can be achieved. [Third Embodiment] The difference between the present embodiment and the first embodiment is that, when the component (A) is prepared, the phenol resin (al) is applied to the phenol resin (a 1 ) % to remove low molecular weight. The point of the phenolic resin (a2) after the body treatment. The base poorly soluble or insoluble resin obtained by reacting the treated phenol resin (a2) with a compound corresponding to the acid dissociable dissolution inhibiting group is used as the component (A). In the present embodiment, a method of treating a low molecular weight, for example, a method of purifying a phenolic aldehyde resin (a 1 ) using an ion exchange resin or the like is used. According to this method, the acid component or the metal component can be removed while removing the low molecular weight body.

Further, the phenol resin (a 1 ) may be first dissolved in a good solvent such as an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, or ethylene glycol monoethyl ether acetate or tetrahydrofuran, and then re-injected. The method of precipitating in water and the like removes the low molecular weight body, respectively. In the course of the synthesis of the phenol resin (al), for example, the content of the dinuclear body or the like can be reduced by steam distillation or the like (JP-A-2000-13185). The yield of the respective removal treatment of the low molecular weight body is preferably in the range of 50 to 95% by mass in the same manner as in the second embodiment. Again, -25- (22) 1296741

The content of the low molecular weight body having an Mw of 500 or less is preferably not more than 12% in the GPC chart. When it is less than 15%, the effect of reducing the heat generation of the photoresist pattern can be achieved, and the effect of reducing the resulting sublimate can be achieved. In the present embodiment, in addition to the resolution and sensitivity of the first embodiment, the thermal conductivity of the positive resist can be further increased. Further, since the low molecular weight bodies are removed, the sublimate added to the % can be reduced. In particular, in the third embodiment, compared with the second embodiment, the solubility of each molecular weight is extremely large, and the low molecular weight body is effectively removed in the yield. [Embodiment] Hereinafter, the present invention will be further described by the following examples, which are not limited by the following examples. On the table, 15 can be used to achieve the same heat resistance when heating, and it can be used for the sake of heat, but this

[Evaluation Method of Positive-Type Photoresist Composition] The evaluation methods of the following (1) to (3) of the positive-type photoresist composition of the following examples or comparative examples are as follows. (1) Sensitivity evaluation: After the positive photoresist composition is rotated on the ruthenium substrate, it is dried on a hot plate at 140 °c (pre-boiled) to form a film thickness of 1.48 μηι. The photoresist is followed by a mask that corresponds to a line and space of 1 · 5 μηι photoresist pattern, and is mirror-finished by a mirror-finisher (a good coating of various physical applicators, 90 seconds of film). 1 能 公司 -26- (23) 1296741, gH ray exposure apparatus), selective exposure of L·amp;S faithfully reproduced exposure amount (Εορ exposure amount) of 1·5 μm. Next, hydrazine was carried out under heating at 140 ° C for 90 seconds. Next, a 23t:, 2.38 mass% THAM aqueous solution (tetramethylammonium hydroxide aqueous solution, product name "NMD-3", manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for development treatment for 90 seconds, and then washed with pure water. After 0 seconds, spin dry.

The indicator for evaluating the sensitivity is the amount of exposure (Εορ, unit: mJ/cm2) that can be faithfully reproduced by L&S of 1.5 μm. (2) Resolution evaluation: Find the critical resolution under the above Εορ exposure. (3) Evaluation of heat resistance: In the above-mentioned Εορ exposure amount, a substrate of L·amp; S having 1·5 μm was placed on a hot plate set at 160 ° C for 1 minute, and the cross-sectional shape thereof was observed. As a result, the dimensional change rate of L&S of 1·5μηι is ±10% or less, and "X" is more than 1 0 〇/〇.

[Production Example of Component (A)] (Production Example 1, without separately removing the treatment step) The phenol resin (a 1 ) is synthesized, and a resin component in which one part of the total phenolic hydroxyl group is protected by ethyl vinyl is prepared ( A 1). However, the treatment for removing the low molecular weight bodies separately was not carried out. That is, in phenolic resin (m·cresol/p-cresol=6/4 (mole ratio)' formalin/salicylaldehyde=3/1 (mole ratio), Mw = 5 5 00 ) ( al ) -27- (24) 1296741 2 〇 mass % solution [solvent = 1,4-dioxane] 250g, adding p-toluenesulfonic acid · monohydrate 〇. 〇 lg, and ethyl vinyl ether 9g, The reaction was carried out at 22 ° C for 2 hours. Next, 0.011 g of triethylamine was added to the reaction liquid, and it was poured into 1 〇〇〇ml of pure water to precipitate a reactant. After filtration, the resulting precipitate was dissolved in 250 g of methanol, and the solution was passed through an ion exchange resin. Thereafter, the solvent was replaced by PGMEA to obtain 125 g of a phenol resin (A1) solution in which 30% of the phenolic hydroxyl group was protected by an ethoxyethyl group.

(Production Example 2, the respective removal treatment steps were carried out after the formation of the protection) The phenol resin (A1) solution obtained in Production Example 1 was prepared to obtain a 30% by mass PGMEA solution, and 270 g of n-heptane was added to the solution. The resulting precipitate was taken out, dissolved in PGMEA, and concentrated to remove n-heptane to obtain a phenol resin (Α2) solution. The yield after separately treatment was 76% by mass, and Mw was 7,200.

(Production Example 3, a separate removal treatment step is applied before the formation of the protection). After the treated phenol resin (a2) obtained by separately treating the low molecular weight body of the phenol resin, the treated phenol resin (a2) is produced. a part of the total phenolic hydroxyl group protected by ethyl vinyl (A3) 〇 ie, the acid bismuth resin (m - A / p - a discretion = 6 / 4 (mr ratio), formaldehyde Water/salicylaldehyde 2/1 (mole ratio), Mw=5 5 00 ) (al) dissolved in methanol and prepared into 150 g of 30% by mass methanol solution, after adding 1 1 5 § pure water A precipitate was obtained. The obtained precipitate was dissolved in 1,4-di-28-(25) 1296741 methane, and concentrated to remove water to obtain a phenol resin (a2) solution. > The yield after treatment was 80% by mass. , respectively, the treated 20% by mass solution of the treated phenolic resin (a2) [solvent di1,4-dioxane] 180g, p-toluenesulfonic acid monohydrate O.Olg, and ethyl vinyl The ether was 6-5 g and reacted at 22 ° C for 2 hours. Next, 0·〇 1 g of triethylamine was added to the reaction liquid, and it was poured into 100 ml of pure water to precipitate a reaction. After filtration, the obtained % precipitate was dissolved in 250 g of methanol, and the solution was passed through an ion exchange resin. Thereafter, the solvent is replaced by PGMEA to obtain a resin component (A3) in which 30% of the total phenolic hydroxyl group of the phenol resin (a2) is protected by ethylvinyl group. - (Production Examples 4 to 6). In Production Examples 1 to 3, a condensing agent (formaldehyde water/salicylaldehyde = 3/1 (mole ratio)) was changed to a mixture of formal water and P-hydroxybenzaldehyde. Resin components (A 4 ) to (A 6 ) were produced in the same manner except for formaldehyde water/p-hydroxybenzaldehyde 2/1 (mole ratio). (Manufacturing Examples 7 to 9) In Production Example 1 To 3, the condensing agent (formaldehyde water/salicylaldehyde 2/1 (mole ratio)) is changed to a mixture of formalin and 3,4-dihydroxybenzaldehyde (formaldehyde water/3,4-dihydroxybenzene) Resin components (A7) to (A9) were produced in the same manner as in the case of aldehyde = 3/1 (mole ratio). (Comparative Example Manufacturing Example 1) -29- (26) 1296741 In Is Example 1 'The condensing agent (formaldehyde water / salicylic acid = 3 / 1 (Wu ^ ear ratio)) was changed to formaldehyde water, and the others were prepared in the same manner, and the resin component (A 1 0 ). (Examples 1 to 9) And Comparative Example 1) 100 parts by mass of the components (A1) to (A10) obtained separately from the above Production Examples 1 to 9 and Comparative Example Production Example 1, (C) component [Upper % (j) Compound]: 3 parts by mass, and (D) component [3-η·fluorenyl group Amine]: 0.2 parts by mass of XR-104 (manufactured by Dainippon Ink Co., Ltd.) dissolved in PGM oxime and added with a surfactant, and after being adjusted to a solution of 35% by mass, membrane filtration using a pore size of μ 2 μηι The filter was filtered to prepare a 'photoresist composition.' The results of the photoresist composition were evaluated in accordance with the crop properties (1) to (3) above, and the results are shown in Table 1 below.

-30- (27) 1296741 Table 1

Low-molecular weight body removal treatment sensitivity (m J / c m2) Resolution (μΐΏ) Heat resistance Example 1 Μ 25 1.2 〇 Example 2 After protection 25 1 .2 〇 Example 3 Before protection 25 1.2 〇 Example 4 Μ > ν 30 1 · 2 〇 Example 5 After protection 30 1.2 〇 Example 6 Before protection 30 1.2 〇 Example 7 Μ j) \\ 25 1.2 〇 Example 8 After protection 25 1.2 〇 Example 9 Protection before 25 1.2 〇Comparative Example 1 Μ 50 1.5 X

As is apparent from the results of Table 1, Examples 1 to 9 are phenol resins synthesized using an aromatic aldehyde having a phenolic hydroxyl group in a condensing agent, which is displayed when compared with Comparative Example 1 in which only a condensing agent is formal water. Better resolution and heat resistance. Further, in the examples, in particular, in the process of the component (A), Examples 2, 3, 5, 6, 8, and 9 which were separately treated with a low molecular weight body showed better heat resistance. The above is a description of the preferred embodiments of the present invention, but the present invention is not limited to the foregoing embodiments. Additions, omissions, substitutions, and other changes can be made in the scope of the technical idea of the present invention. The present invention is not limited by the foregoing description, and its contents are described in the range of -31 - (28) (28) 1296741 of the appended claims. The present invention can provide an alkali-soluble resin which is a phenolic resin (a1) synthesized by using a hydroxy-substituted aromatic aldehyde as a condensing agent, which can be excellent in alkali solubility of a resin component and can even improve its solubility. Chemically enhanced positive photoresist composition for heat resistance.

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Claims (1)

(1) (1) 1296741 X. Patent Application No. 941 10322 Patent Application Revision of Chinese Patent Application Scope August 1994 1 1 · A chemically amplified positive photoresist composition containing resin components 'and (C) via radiation a strong positive resist composition which is formed by the action of an acid component and an organic solvent, and which has a function of increasing the solubility in an aqueous alkali solution by the action of the component produced by the above (C) component, and is characterized in that The above component (A) contains an aromatic hydroxy compound, - a formaldehyde containing a total amount of aldehyde of 50 to 90%, and an aldehyde substituted with a total of 10 to 50 mol% of a hydroxy-substituted aromatic aldehyde. a resin which is insoluble or insoluble in alkali which is partially protected by an acid dissociation inhibitor by a portion of the total phenolic hydroxyl group of the phenol resin (a1), which is condensed in an amount of 50 to 100 mol% relative to the aromatic hydroxy compound. . 2. The chemically-enhanced positive-type photo-product of claim 1, wherein the (Α) component contains the phenolic resin (one of the total phenolic hydroxyl groups is poorly protected by an acid dissociable dissolution inhibiting group) In the insoluble resin, the resin component obtained by removing the low molecular weight is respectively applied. 3. The chemically amplified positive photoactive material according to the first aspect of the patent application, wherein the component (A) is an aromatic hydroxy compound, and comprises formaldehyde. The aldehyde of the hydroxy-substituted aromatic aldehyde is subjected to a condensation reaction, and the acidity of the combined acid of the modified (A) is increased by at least the aldehyde content of the aryl group obtained by the above-mentioned aromatic dissolution resistance composition a). Phenol (2) 1296741 aldehyde resin containing a portion of the total phenolic hydroxyl group of the phenolic resin (a2) obtained by removing the low molecular weight body, respectively, which is poorly soluble by an acid dissociable dissolution inhibiting group or Insoluble resin component.