JPH07271022A - Positive photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a positive photoresist compsn. for superfine processing having high resolution and little dependence of the resolution on the film thickness by using an alkali-soluble resin and a quinone diazide compd. having a specified mother nucleus structural formula. CONSTITUTION:This compsn. contains an alkali-soluble resin and 1,2- naphthoquinone diazide-5-(and/or -4-) sulfonate of polyhydroxy compd. having a structure expressed by formula. In formula, Y is -SO2- or -SO2-Z-SO2-, Z is an alkylene group, R1 and R2 may be same or different and are hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups or alkoxy groups, R3-R6 may be same or different and are hydrogen atoms, alkyl groups, or aryl groups, and/m) (n), (o), m', n' are integers 1 to 3. The polyhydroxy compd. as described above is used as a single state or a mixture of two or more kinds.

Description

Detailed Description of the Invention

[0001]

The present invention contains an alkali-soluble resin and a 1,2-quinonediazide compound and is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays and synchrotron radiation. More specifically, the present invention relates to a positive-type photoresist composition, and more specifically, a high-resolution positive-type photoresist having high resolution regardless of film thickness variation, less development residue, and excellent development latitude. It relates to photoresists. The positive photoresist according to the present invention is applied on a substrate such as a semiconductor wafer, glass, ceramics or metal by spin coating or roller coating to a thickness of 0.5 to 2 μm. After that, it is heated and dried, and a circuit pattern or the like is baked through an exposure mask by irradiation of ultraviolet rays or the like, and if necessary, post-exposure baking is performed and then development is performed to form a positive image. Further, etching is performed using this positive image as a mask, whereby patterned processing can be performed on the substrate. Typical fields of application include manufacturing processes for semiconductors such as ICs, manufacturing circuit boards such as liquid crystals and thermal heads, and other photo-ablation processes.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin binder such as novolac and a naphthoquinonediazide compound as a photosensitive material is used. Novolac resin as a binder,
It is particularly useful for this application because it can be dissolved in an alkaline aqueous solution without swelling, and when it is used as a mask for etching, it gives a high resistance to plasma etching. Further, the naphthoquinonediazide compound used for the photosensitive material acts as a dissolution inhibitor which lowers the alkali solubility of the novolak resin by itself, but when it is decomposed by light irradiation, an alkali-soluble substance is produced and rather the alkali solubility of the novolak resin is reduced. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large change in properties with respect to light. From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use. In particular, the progress of resist materials toward high resolution is remarkable, and sufficient results have been achieved in line width processing down to submicrons.

Conventionally, in order to improve the resolution and obtain an image having a good pattern shape, it has been advantageous to use a resist having a high contrast (γ value), and technical development of a resist composition suitable for such a purpose has been carried out. I've been told. There are an extremely large number of publications disclosing such a technique, and particularly for the novolak resin which is a main part of the positive photoresist, many patent applications have been made regarding its monomer composition, molecular weight distribution, synthetic method, etc. Has been achieved. Also, with regard to the photosensitive material which is another main component, compounds having many structures which are effective for increasing the contrast have been disclosed. By designing a positive photoresist using these techniques, it has become possible to develop an ultrahigh resolution resist capable of resolving a pattern having a size comparable to the wavelength of light.

However, integrated circuits are becoming more and more integrated, and it is necessary to process an ultrafine pattern having a line width of 0.5 μm or less in the production of a semiconductor substrate such as a VLSI. Is becoming. In such applications, particularly stable and high resolution is obtained,
There is a demand for a photoresist having a wide development latitude in order to always secure a constant processing line width. Further, it is required that no resist residue is generated in the resist pattern after development in order to prevent circuit processing defects.

Further, particularly in the formation of an ultrafine pattern of 0.5 μm or less, for example, even if a certain resolution is obtained with a certain coating film thickness, it can be obtained by slightly changing the coating film thickness. Phenomenon that resolution deteriorates (hereinafter,
It is known that there is "film thickness dependency"). Surprisingly, the resolving power changes greatly even if the film thickness changes by only a few hundredths of μm, and more or less than any of the typical positive photoresists currently on the market. I also found that there was a tendency. Specifically, when the thickness of the resist film before exposure changes within a range of λ / 4n (λ is the exposure wavelength, n is the refractive index of the resist film at that wavelength) with respect to the predetermined film thickness, The resolution that is applied varies. The problem of this film thickness dependence is, for example, SPIE Proceedings Vol. 1925, p. 626 (1993).
The existence thereof is pointed out and it is stated that this is caused by the multiple reflection effect of light in the resist film.

Here, when actually processing a semiconductor substrate, a pattern is formed by using a resist film applied with a film thickness slightly different depending on the location due to unevenness on the substrate surface or unevenness of the coating film thickness. Will be done. Therefore, this film thickness dependence has been one obstacle in carrying out fine processing close to the limit of its resolution using a positive photoresist.

To date, a large number of 1,2-naphthoquinonediazide compounds, which are polyhydroxy compounds having a specific structure, have been proposed in order to enhance the resolution. For example,
JP-A-57-63526, 60-163043, and 6
2-10645, 62-2, 10646, 62-150.
245, 63-220139, 64-76047,
JP-A-1-189644, 2-285351, 2-
296248, 2-296249, 3-4824
9, Same 3-48250, Same 3-158856, Same 3-2
28057, Japanese Patent Publication No. 4-502519, US Patent 495.
7846, 4992356, 5151340, 5
178986, European Patent 530148, etc. However, even if these photosensitive materials are used, they are insufficient from the viewpoint of reducing the film thickness dependency.

On the other hand, by using a photosensitive material having a hydroxyl group in the molecule, a resist having high contrast and high resolution can be obtained, for example, as described in JP-B-37-18.
015, JP-A-58-150948, JP-A-2-198.
46, ibid. 2-103543, ibid. 3-228057, ibid. 5
-323597, European Patent 573056, US Patent 31
84310, 3188210, 3130047, 3130048, 3130049, 310280.
9, 3061430, 3180733, West German patent 9
38233, SPIE Proceedings 631, 210, 1672.
Volume 231 (1992), 1167, 262 (1992) and 1
Vol. 925, p. 227 (1993). Although it is possible to increase the contrast by using the resist containing the photosensitive material described in these publications, it is not sufficient from the viewpoint of reducing the film thickness dependency. As described above, it has never been known how to design the resist material so as to reduce the film thickness dependency and obtain a high resolution regardless of the film thickness.

Further, as semiconductors are highly integrated, the demand for particles of positive photoresist is increasing more and more. In semiconductors, as is generally said to be 1/10 rule, 1 / min of the minimum line width of device
Particles of 10 or more size affect yield (Ultra Clean Technology, Vol.3, No.1, P79 (1991)
etc). In order to reduce the particles, measures such as using an ultrafine filter having pore diameters of 0.1 μm and 0.05 μm have been made at the time of manufacturing the resist, which is useful for reducing the particles at the time of manufacturing the resist.

However, even if the number of particles is small at the time of manufacture, the number of particles often increases as the resist ages. Most of the particles due to the passage of time are caused by the 1,2-quinonediazide photosensitive material, and various improvements have been made so far in order to improve the passage of time. For example, a method using a photosensitizer in which a part of the hydroxyl groups of a polyhydroxy compound is acylated or sulfonylated (JP-A-62-17856).
2), a method using a mixture of 1,2-naphthoquinonediazide-4-sulfonic acid ester and -5-sulfonic acid ester (JP-A-62-284354), heat-modified 1,
A method using a 2-naphthoquinonediazide photosensitizer (JP-A-63-113451), a method of reducing the residual catalyst of the photo-sensitizer (JP-A-63-236030), and a method of synthesizing the photo-sensitizer in the presence of an anion exchange resin. (JP-A-63-236
031), and a method of further mixing a solvent having excellent solubility with respect to the photosensitizer (JP-A-61-260239, JP-A1-2).
93340) has been tried so far.

[0011]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a positive photoresist composition for ultrafine processing, which has a high resolving power and has a small film thickness dependence of the resolving power. In the present invention, the term "thickness dependence" means the resolution of a resist obtained by exposure and (baking if necessary) development when the resist film thickness before exposure changes in the range of λ / 4n. Say fluctuations. A second object of the present invention is to provide a positive photoresist composition having a wide development latitude and being less prone to development residues. Here, the development latitude can be expressed by the development time dependency of the resist line width obtained by development or the temperature dependency of the developing solution. The development residue refers to a trace amount of resist insoluble matter that remains between fine patterns after development, which can be observed with a scanning electron microscope or the like. A third object of the present invention is to prevent the precipitation of photosensitizer and the generation of microgels over time, that is,
An object of the present invention is to provide a positive photoresist composition having extremely excellent storage stability in which no increase in particles is observed.

[0012]

Means for Solving the Problems As a result of intensive investigations by the present inventors, taking into account the above-mentioned various characteristics, it was found that an alkali-soluble resin
It has been found that the above problems can be solved by using a quinonediazide compound having a specific mother nucleus structural formula, and the present invention has been completed based on this finding. That is, an object of the present invention is to provide an alkali-soluble resin and a 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of a polyhydroxy compound having a structure represented by the following general formula (I). It was achieved by a positive photoresist composition characterized by containing.

[0013]

[Chemical 2]

Here, Y: —SO ₂ — or —SO ₂ —Z—SO ₂ —, Z: an alkylene group, R ₁ and R ₂ : may be the same or different, and are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group. Group or alkoxy group, R _{3 to} R ₆ : may be the same or different, and represent a hydrogen atom, an alkyl group or an aryl group, m, n, o, m ′, n ′: an integer of 1 to 3. Hereinafter, the present invention will be described in detail.

In R ₁ and R ₂ of the above general formula (I), the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom, and the alkyl group is a methyl group, an ethyl group, a propyl group, an isopropyl group or n-. An alkyl group having 1 to 4 carbon atoms such as a butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group is preferable, and a methyl group is particularly preferable. As the alkoxy group, methoxy group, ethoxy group, propoxy group, isopropoxy group, n
An alkoxy group having 1 to 4 carbon atoms such as -butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group is preferable, and a methoxy group is particularly preferable.

In R _{3 to} R ₆ , the alkyl group is preferably a methyl group or an ethyl group, and the aryl group is preferably a substituted or unsubstituted aryl group. A phenyl group, an o-hydroxyphenyl group, an m-hydroxyphenyl group and a p-group are preferable. −
Hydroxyphenyl groups are particularly preferred. Moreover, in Y of the general formula (I), the alkylene group has 1 to 1 carbon atoms.
An alkylene group of 4 is preferred.

Specific examples of the polyhydroxy compound having the structure represented by the general formula (I) include the following [I-1] to
The compound represented by [I-12] may be mentioned, but the compound usable in the present invention is not limited thereto. These polyhydroxy compounds may be used alone or in admixture of two or more.

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

The above general formula [I-1] or [I-2]
The compound (modified phenolic resin) represented by is obtained by copolymerizing dicyclopentadiene and phenols in excess thereof with a Lewis acid. The dicyclopentadiene may have a purity of 90% or more, and may contain butadiene, isoprene and the like as impurities. The purity is preferably 95% or more. Examples of phenols include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol,
Xylenols such as 3,4-xylenol and 2,3-xylenol, alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol and pt-butylphenol, 2,3,5-trimethylphenol, Trialkylphenols such as 2,3,4-trimethylphenol, p-methoxyphenol, m
-Methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol, etc. Alkoxyphenols, m-chlorophenol, p-chlorophenol, o-chlorophenol, catechol, resorcinol, hydroquinone and the like are preferably used. These phenols may be used alone or as a mixture. These may be of any purity as long as they are used industrially, and may not be any special ones.

The Lewis acid used as a catalyst for polymerization and condensation includes AlCl ₃ , BF ₃ , ZnCl ₂ , H ₂ SO ₄ , and TiC.
l ₄ , H ₃ PO _{4 and the} like can be mentioned, and these catalysts can be used alone or as a mixture. Preferably, it is desirable to use BF ₃ alone.

Polymerization of dicyclopentadiene and phenols is carried out in a molten state or in a suitable solvent solution. As the solvent at this time, benzene, toluene,
Xylene etc. can be mentioned. As the polymerization method,
The Lewis acid may be added dropwise to the mixture of dicyclopentadiene and phenol, or dicyclopentadiene may be added dropwise to the mixture of phenol and Lewis acid. The dropping time may be several minutes to several hours, and the post-reaction may be carried out for several hours after the dropping. The reaction temperature at this time is 20 to 18
0 ° C is good, and preferably 60 to 120 ° C.

The compounds represented by the above general formulas [I-4] to [I-6] (modified phenol resin) can be synthesized by two production methods. The manufacturing method will be specifically described below. In the first production method, as described above, dicyclopentadiene and phenols in excess of this are copolymerized using a Lewis acid (first step reaction), and then excess phenols are condensed with aldehydes ( Second stage reaction)
Is the way. Condensation of residual phenols with aldehydes, which is the second step of the reaction, can be carried out subsequently to the reaction of the first step, and is carried out in the molten state or in a suitable solvent. At this time, a solvent may be newly added, and examples of the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and tetrahydroterane in addition to the above-mentioned solvents.
At this time, a small amount of water may be added to decompose the Lewis acid, and a Lewis acid or an acid catalyst such as hydrochloric acid, phosphoric acid or oxalic acid may be newly added.

As the aldehydes, paraformaldehyde, formaldehyde aqueous solution and the like can be used. When paraformaldehyde is used, it may be dissolved in a solvent and added dropwise, or it may be added as a solid in several divided portions, and when an aqueous formaldehyde solution is used, it may be added dropwise in several minutes to several hours. The reaction temperature at this time may be in the same range as in the first stage reaction, but may be a temperature different from that in the first stage reaction. As described above, this production method is characterized in that the polymerization of the dicyclopentadiene-modified phenol resin (first-stage reaction) and the condensation of the phenols with the aldehydes (second-stage reaction) are carried out continuously. Thereafter, residual phenols are removed from the reaction solution by distillation under reduced pressure, diluted with a solvent to a predetermined concentration, and then the ions are mainly washed and removed using ion-exchanged water. After that, the solvent used for the reaction and washing is distilled off under reduced pressure and cooled to obtain a solid title modified phenol resin.

Next, the second manufacturing method will be described.
This is a method in which phenols and aldehydes are added to the above-mentioned dicyclopentadiene-modified phenol resin and co-condensed with an acid catalyst. As the dicyclopentadiene, phenols and aldehydes, those mentioned above are used. As the acid catalyst, hydrochloric acid, phosphoric acid, oxalic acid, sulfuric acid or the like is used. The reaction can be carried out in a molten state or in a solution, but is carried out by adding aldehydes to a mixture of dicyclopentadiene-modified phenol resin and phenols.
The addition of aldehydes may be as described above. The reaction temperature is preferably in the range of 20 to 180 ° C, preferably 60 to 1
It is 20 ° C. The addition time of the aldehydes is several minutes to several hours, but when the addition amount is large, it is desirable to add the aldehydes slowly so as not to cause a rapid heat generation. After the reaction, distillation of the phenols, washing, removal of the solvent and the like can be carried out in the same manner as the above-mentioned method to obtain a solid modified phenol resin.

The compound represented by the formula [I-3] can be obtained by, for example, the method described in US Pat. No. 3,567,683, that is, p-cresol and dicyclopentadiene in toluene solvent as P.
It can be synthesized using a catalyst such as Cl ₃ .

The compounds represented by the formulas [I-7] to [I-11] (modified phenol resin) are, for example, 4-vinylcyclohexene and / or 5-vinyl norbornene and the above-mentioned phenols as an acid catalyst. It is obtained by reacting in the presence. 4-Vinylcyclohexene and 5-vinylnorbornene are compounds that are easily obtained by the Diels-Alder reaction between butadiene and cyclopentadiene. At this time, 4-vinylcyclohexene and 5-vinylnorbornene can be used alone, respectively, and when they are mixed and used, the weight ratio thereof is 100: 1 to 1: 1.
A ratio in the range of 00 is preferable.

4-vinylcyclohexene and / or 5-
The acid catalyst used when reacting vinyl norbornene with phenols includes boron trifluoride, boron trifluoride ether complex, water complex, amine complex, phenol complex or alcohol complex, etc. Aluminum compounds such as aluminum and diethyl aluminum monochloride, iron chloride, titanium tetrachloride, sulfuric acid,
Hydrogen fluoride, trifluoromethane sulfonic acid and the like can be preferably used, and particularly from the viewpoint of activity and easy removal of catalyst, boron trifluoride, boron trifluoride ether complex, boron trifluoride phenol complex, A boron trifluoride water complex, a boron trifluoride alcohol complex, and a boron trifluoride amine complex are preferable, and further, a boron trifluoride and a boron trifluoride phenol complex are most preferable. The amount of the acid catalyst used varies depending on the catalyst used. For example, in the case of a boron trifluoride phenol complex, it is 0.1 to 100 parts by weight of 4-vinylcyclohexene and / or 5-vinylnorbornene. It is preferably 20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

The above reaction can be carried out with or without a solvent. When no solvent is used, the charged amount of phenols is 4-vinylcyclohexene and / or
Further, it is preferable to use an equivalent amount or more, especially 3 to 10 times equivalent amount based on the charged amount of 5-vinylnorbornene. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit the reaction, and for example, aromatic hydrocarbon compounds such as benzene, toluene and xylene can be preferably used. .

The reaction temperature varies depending on the type of catalyst used, but for example, when a boron trifluoride phenol complex is used, it is preferably 20 to 170 ° C, more preferably 40 to 150 ° C. If the reaction temperature exceeds 170 ° C, decomposition or side reaction of the catalyst occurs, and if it is less than 20 ° C, the reaction is slow and economically disadvantageous.

When the method of sequentially adding 4-vinylcyclohexene and / or 5-vinylnorbornene in carrying out the above reaction, homopolymerization of 4-vinylcyclohexene and / or 5-vinylnorbornene is used. Can also be prevented.

In the above reaction, the modified phenol resin can be obtained by filtering or deactivating the catalyst after completion of the reaction and then concentrating the resulting solution. The method for removing the catalyst varies depending on the type of the catalyst used. For example, in the case of boron trifluoride phenol complex, the catalyst is added by adding calcium hydroxide, magnesium hydroxide or the like in a molar amount 1 to 10 times that of the catalyst. After deactivation, the catalyst is preferably filtered. In addition, it is desirable to improve the workability by adding a solvent or raising the temperature of the filtered product during the filtration.

The compound represented by the formula [I-12] (modified phenol resin) can be obtained by, for example, the method described in European Patent 340705, that is, bis (dihydrodicyclopentadienyl) obtained from dicyclopentadiene and hydrogen sulfide. ) -Sulfide is oxidized to give bis (dihydrodicyclopentadienyl) -sulfone, which is obtained by reacting this with phenol in the presence of an acid catalyst.

The photosensitive material of the present invention includes, for example, the polyhydroxy compound resin and 1,2-naphthoquinonediazide-5-
(And / or -4-) sulfonyl chloride can be obtained by carrying out an esterification reaction in the presence of a basic catalyst. That is, a predetermined amount of polyhydroxy compound resin and 1,
2-naphthoquinonediazide-5- (and / or -4-)
A solvent such as sulfonyl chloride, dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, trichloroethane, dichloroethane or γ-butyl lactone is charged into the flask and a basic catalyst such as sodium hydroxide, sodium carbonate, hydrogen carbonate is added. Sodium, triethylamine, 4-
Dimethylaminopyridine, 4-methylmorpholine, N-
Methylpiperazine, N-methylpiperidine and the like are added dropwise for condensation. The obtained product is crystallized in water, washed with water, and further purified and dried.

In the usual esterification reaction, a mixture having various esterification numbers and esterification positions can be obtained. However, if a synthesis condition or a structure of a polyhydroxy compound is selected, only a specific isomer is selectively selected. It can also be esterified. The esterification rate in the present invention is defined as the average value of this mixture. The esterification rate defined in this way is calculated from the raw material polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or-
4-) It can be controlled by the mixing ratio with sulfonyl chloride. That is, the added 1,2-naphthoquinonediazide-
Substantially all of the 5- (and / or -4-) sulfonyl chloride undergoes an esterification reaction. Therefore, in order to obtain a mixture having a desired esterification rate, the molar ratio of the raw materials may be adjusted.

If necessary, 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid ester may be used in combination. The reaction temperature in the above method is usually -20.
C. to 60.degree. C., preferably 0.degree. C. to 40.degree.

When the photosensitive compound of the present invention synthesized by the above-mentioned method is used as a resin composition, it may be used alone or as a mixture of two or more kinds thereof in an alkali-soluble resin. The blending amount is 100% Novolac resin.
5 to 100 parts by weight of the photosensitive material, preferably 2 parts by weight
It is 0 to 60 parts by weight. If the usage ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and if it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are lowered.

Examples of the alkali-soluble resin used in the present invention include novolak resin, acetone-pyrogallol resin, polyhydroxystyrene and derivatives thereof. Among these, novolak resin is particularly preferable,
It can be obtained by addition-condensing an aldehyde with a predetermined monomer as a main component in the presence of an acidic catalyst. As the predetermined monomer, phenol, m-cresol, p
-Cresols, cresols such as o-cresol, 2,
Xylenols such as 5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol,
alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, 2,3,5-trimethylphenol,
Trialkylphenols such as 2,3,4-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol , M-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol, and other alkoxyphenols, 2-methyl-4-isopropylphenol, and other bisalkylphenols, m-chlorophenol, p-chlorophenol. , O-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol,
Hydroxy aromatic compounds such as resorcinol and naphthol may be used alone or in combination of two or more, but are not limited thereto.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p. -Hydroxybenzaldehyde, o-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, and of these, formaldehyde is preferably used. These aldehydes are
They may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used.

Further, JP-A-60-45238 and 60-
97347, 60-140235, 60-1897.
39, 64-14229, JP-A-1-276131,
2-60915, 2-275955, 2-282
745, 4-101147, 4-122938, etc., that is, it is preferable to use a technique in which low-molecular components of novolac resin are removed or reduced.

The weight average molecular weight of the thus obtained novolak resin is preferably in the range of 2000 to 20000. If it is less than 2000, the film loss of the unexposed area after development is large, and if it exceeds 20000, the developing speed becomes slow. The range of 3000 to 15000 is particularly preferable. Here, the weight average molecular weight is defined as having a polystyrene conversion value of gel permeation chromatography. Further, the dispersity of the novolac resin (the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, that is, Mw / Mn) is preferably from 1.5 to 7.0, more preferably 1.
It is 5 to 4.0. If it exceeds 7, the effect of the present invention that the film thickness dependency is good cannot be obtained, while if it is less than 1.5, a high purification step is required for synthesizing the novolac resin, so that it is practically practical. Improper due to lack.

In the present invention, the above-mentioned photosensitive material should be used, but if necessary, 1,2-naphthoquinonediazide-5- (and / or-) of the polyhydroxy compound shown below is used.
4-) An esterified product with sulfonyl chloride can be used in combination. At this time, the ratio of the naphthoquinone diazide ester photosensitive material of these polyhydroxy compounds to the photosensitive material of the present invention is preferably 20/80 to 80/20 (weight ratio). That is, if the photosensitive material of the present invention is less than 20% by weight of the total photosensitive material, the effect of the present invention cannot be sufficiently exhibited.

Examples of polyhydroxy compounds include 2,
3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2 '
-Methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,6,3', 4'-penta Hydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 5'-pentahydroxybenzophenone, 2,4,6,3 ', Polyhydroxybenzophenones such as 4 ′, 5′-hexahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone,

Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenyl pentyl ketone, 2,3,4-trihydroxyphenylhexyl ketone,

Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane-
1, bis ((poly) hydroxyphenyl) alkanes such as bis (2,3,4-trihydroxyphenyl) propane-1, nordihydroguaiaretic acid,

Propyl 3,4,5-trihydroxybenzoate Phenyl 2,3,4-trihydroxybenzoate 3,
Polyhydroxybenzoic acid esters such as phenyl 4,5-trihydroxybenzoate,

Bis (2,3,4-trihydroxybenzoyl) methane, bis (3-acetyl-4,5,6-trihydroxyphenyl) -methane, bis (2,3,4-trihydroxybenzoyl) benzene, Bis (polyhydroxybenzoyl) alkanes such as bis (2,4,6-trihydroxybenzoyl) benzene or bis (polyhydroxybenzoyl) aryls,

Ethylene glycol-di (3,5-dihydroxybenzoate), ethylene glycol-di (3,5
Alkylene-di (polyhydroxybenzoates) such as 4,5-trihydroxybenzoates),

2,3,4-biphenyltriol, 3,4,
5-Biphenyltriol 3,5,3 ', 5'-biphenyl tetrol, 2,4,2', 4'-biphenyl tetrol, 2,4,6,3 ', 5'-biphenyl Pentore, 2,4,
6,2 ', 4', 6'-biphenylhexol, 2,3,4,
Polyhydroxybiphenyls such as 2 ′, 3 ′, 4′-biphenylhexol,

Bis (polyhydroxy) sulfides such as 4,4'-thiobis (1,3-dihydroxy) benzene,

Bis (polyhydroxyphenyl) ethers such as 2,2 ', 4,4'-tetrahydroxydiphenyl ether,

Bis (polyhydroxyphenyl) sulfoxides such as 2,2 ', 4,4'-tetrahydroxydiphenylsulfoxide,

Bis (polyhydroxyphenyl) sulfones such as 2,2 ', 4,4'-diphenyl sulfone,

Tris (4-hydroxyphenyl) methane, 4,4 ', 4 "-trihydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 4,4 ', 3", 4''-Tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4 ', 2'',3'',4''-pentahydroxy-3,5,3', 5 ' -Tetramethyltriphenylmethane, 2,3,4,2 ', 3', 4'-hexahydroxy-5,
5'-diacetyltriphenylmethane, 2,3,4,2 ',
3 ', 4', 3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2 ', 4', 6'-hexahydroxy-5,5'- Polyhydroxytriphenylmethanes such as dipropionyltriphenylmethane,

3,3,3 ', 3'-tetramethyl-1,1'-
Spirobi-indan-5,6,5 ', 6'-tetrol, 3,
3,3 ′, 3′-tetramethyl-1,1′-spirobi-indane-5,6,7,5 ′, 6 ′, 7′-hexool, 3,3,3 ′,
3'-tetramethyl-1,1'-spirobi-indane-4,
5,6,4 ', 5', 6'-Hexool, 3,3,3 ', 3'-tetramethyl-1,1'-spirobi-indane-4,5,6,
Polyhydroxyspirobi-indanes such as 5 ′, 6 ′, 7′-hexool,

3,3-bis (3,4-dihydroxyphenyl) phthalide, 3,3-bis (2,3,4-trihydroxyphenyl) phthalide, 3 ', 4', 5 ', 6'- Polyhydroxyphthalides such as tetrahydroxyspiro [phthalide-3,9′-xanthene],

Flavono pigments such as morin, quercetin and rutin,

Α, α ', α "-tris (4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,
α ′, α ″ -tris (3,5-dimethyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene,
α, α ', α "-tris (3,5-diethyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α', α" -tris (3,5-di-n-propyl) −
4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-diisopropyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ', α "-Tris (3,5-
Di-n-butyl-4-hydroxyphenyl) 1,3,5-
Triisopropylbenzene, α, α ', α "-tris (3
-Methyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ', α "-tris (3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α , Α ', α "-Tris (2,4-
Dihydroxyphenyl) 1,3,5-triisopropylbenzene, 1,3,5-tris (3,5-dimethyl-4)
-Hydroxyphenyl) benzene, 1,3,5-tris (5-methyl-2-hydroxyphenyl) benzene,
2,4,6-Tris (3,5-dimethyl-4-hydroxyphenylthiomethyl) mesitylene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4-
[Α, α'-bis (4 "-hydroxyphenyl) ethyl]
Benzene, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -3- [α, α'-bis (4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl- α- (3 ′, 5′-dimethyl-4′-hydroxyphenyl) ethyl] -4- [α, α′-bis (3 ″, 5 ″ -dimethyl-4 ″ -hydroxyphenyl) ethyl] benzene,
1- [α-methyl-α- (3'-methyl-4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (3 "-
Methyl-4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (3'-methoxy-4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (3 "-Methoxy-4" -hydroxyphenyl) ethyl]
Benzene, 1- [α-methyl-α- (2 ′, 4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1-
[Α-Methyl-α- (2 ′, 4′-dihydroxyphenyl) ethyl] -3- [α ″, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene and the like JP-A-4-2530
58. A polyhydroxy compound according to 58,

P-bis (2,3,4-trihydroxybenzoyl) benzene, p-bis (2,4,6-trihydroxybenzoyl) benzene, m-bis (2,3,4-trihydroxybenzoyl) benzene , M-bis (2,4,6-
Trihydroxybenzoyl) benzene, p-bis (2,
5-dihydroxy-3-bromobenzoyl) benzene,
p-bis (2,3,4-trihydroxy-5-methylbenzoyl) benzene, p-bis (2,3,4-trihydroxy-5-methoxybenzoyl) benzene, p-bis (2,3,4-) Trihydroxy-5-nitrobenzoyl)
Benzene, p-bis (2,3,4-trihydroxy-5-
Cyanobenzoyl) benzene, 1,3,5-tris (2,
5-dihydroxybenzoyl) benzene, 1,3,5-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,3-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2 , 4-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,4,5-tetrakis (2,3,4-trihydroxybenzoyl) benzene, α, α′-bis (2,3, 4-trihydroxybenzoyl) -p-xylene, α, α ′, α′-tris (2,3,4-
Trihydroxybenzoyl) mesitylene,

2,6-bis- (2'-hydroxy-3 ',
5'-dimethyl-benzyl) -p-cresol, 2,6
-Bis- (2'-hydroxy-5'-methyl-benzyl)
-P-cresol, 2,6-bis- (2'-hydroxy-3 ', 5'-di-t-butyl-benzyl) -p-cresol, 2,6-bis- (2'-hydroxy-5') -Ethyl-benzyl) -p-cresol, 2,6-bis-
(2 ', 4'-Dihydroxy-benzyl) -p-cresol, 2,6-bis- (2'-hydroxy-3'-t-butyl-5'-methyl-benzyl) -p-cresol, 2,
6-bis- (2 ', 3', 4'-trihydroxy-5'-acetyl-benzyl) -p-cresol, 2,6-bis-
(2 ', 4', 6'-trihydroxy-benzyl) -p-
Cresol, 2,6-bis- (2 ', 3', 4'-trihydroxy-benzyl) -p-cresol, 2,6-bis- (2 ', 3', 4'-trihydroxy-benzyl)-
3,5-Dimethyl-phenol, 4,6-bis- (4 '
-Hydroxy-3 ', 5'-dimethyl-benzyl) -pyrogallol, 4,6-bis- (4'-hydroxy-3',
5'-dimethoxy-benzyl) -pyrogallol, 2,6
-Bis- (4'-hydroxy-3 ', 5'-dimethyl-benzyl) -1,3,4-trihydroxy-phenol,
4,6-bis- (2 ', 4', 6'-trihydroxy-benzyl) -2,4-dimethyl-phenol, 4,6-bis- (2 ', 3', 4'-trihydroxy-benzyl) ) −
2,5-dimethyl-phenol and the like can be mentioned.

Further, it is also possible to use a low-nuclear substance of a phenol resin such as a novolak resin.

The composition of the present invention may further contain a polyhydroxy compound in order to accelerate the dissolution in the developing solution. Preferred polyhydroxy compounds include phenols, resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phloroglucide, 2,4,2', 4'-biphenyl tetrol, 4,4'-thiobis (1,3-dihydroxy) benzene 2,2 ', 4,4'-Tetrahydroxydiphenyl ether, 2,2', 4,4'-Tetrahydroxydiphenyl sulfoxide, 2,2 ', 4,4'-Tetrahydroxydiphenyl sulfe Fluorine, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 ′-(α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris ( -
Hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,
2,2-tris (hydroxyphenyl) propane, 1,
1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-
Hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α,
α ′, α′-tetrakis (4-hydroxyphenyl)]-
Xylene etc. can be mentioned. These polyhydroxy compounds can be added in an amount of usually 100 parts by weight or less, preferably 70 parts by weight or less, and more preferably 50 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin.

Solvents for dissolving the photosensitive material and the alkali-soluble novolak resin of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol. Methyl ether acetate, propylene glycol propyl ether acetate, toluene,
Xylene, methyl ethyl ketone, cyclohexanone, 2
-Ethyl hydroxypropionate, 2-hydroxy-2
-Ethyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Methyl, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate and the like can be used. These organic solvents are used alone or in combination of two or more.

Furthermore, N-methylformamide, N, N-
Dimethylformamide, N-methylacetamide, N,
A high-boiling solvent such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether can be mixed and used.

A surfactant may be added to the positive photoresist composition of the present invention in order to further improve the coating properties such as striation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonyl Polyoxyethylene alkyl allyl ethers such as phenol ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristea Sorbitan fatty acid esters such as oleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., polyoxyethylene sorbitan fatty acid esters nonionic surface active agents such as, Efutotsupu EF
301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.)
Manufactured), Megafasc F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
SC104, SC105, SC106 (Made by Asahi Glass Co., Ltd.)
Fluorine-containing surfactants such as organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 7
5, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. Among these surfactants, fluorine-based surfactants and silicon-based surfactants are particularly preferable. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the alkali-soluble resin and the quinonediazide compound in the composition of the present invention. These surfactants may be added alone or in some combinations.

The developer for the positive photoresist composition of the present invention includes sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, triethylamine and methyldiethylamine. Tertiary amines such as
Uses an aqueous solution of alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine, etc. can do. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts.

The positive photoresist composition of the present invention may contain a light absorber, a cross-linking agent, an adhesion aid, etc., if necessary. The light absorber is added as necessary for the purpose of preventing halation from the substrate and for improving the visibility when applied to the transparent substrate. For example, commercially available light absorbers described in "Technology and Markets of Industrial Dyes" (CMC Publishing) and the Handbook of Dyes (Edited by Synthetic Organic Chemistry), such as CIDe.
sperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,56,
60,64,66,68,79,82,88,90,93,102,114 and 124, CIDis
perse Orange 1,5,13,25,29,30,31,44,57,72 and 73, C.
I. Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,7
3,88,117,137,143,199 and 210, CIDisperse Violet 4
3, CIDisperse Blue 96, CI Fluorescent Brighteni
ng Agent112, 135 and 163, CI Solvent Yellow 14,16,
33 and 56, CISolvent Orange2 and 45, CISolvent
Red 1,3,8,23,24,25,27 and 49, CI Pigment Green 1
0, CI Pigment Brown 2 and the like can be preferably used. The light absorber is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin,
More preferably, it is blended in a proportion of 30 parts by weight or less.

The crosslinking agent is added within a range that does not affect the formation of a positive image. The purpose of adding the crosslinking agent is mainly
These include sensitivity adjustment, improvement of heat resistance, and improvement of dry etching resistance. Examples of the cross-linking agent include melamine, benzoguanamine, glycoluril, etc., which are reacted with formaldehyde, or their alkyl modified products, epoxy compounds, aldehydes, azide compounds, organic peroxides, hexamethylenetetramine, etc. be able to. These cross-linking agents can be added in an amount of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the photosensitizer. If the amount of the cross-linking agent is more than 10 parts by weight, the sensitivity is lowered and scum (resist residue) is generated, which is not preferable.

The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate and the resist and preventing the resist from being peeled off particularly in the etching step. Specific examples include trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chlorosilanes such as chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane,
Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole, vinyltrichlorosilane, γ-
Silanes such as chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-
Heterocyclic compounds such as mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, and urea such as 1,1-dimethylurea and 1,3-dimethylurea, and Can include thiourea compounds. These adhesive aids are usually used in an amount of 10 parts by weight per 100 parts by weight of the alkali-soluble resin.
The amount is less than 5 parts by weight, preferably less than 5 parts by weight.

A spinner or coater is provided on a substrate (eg, a silicon / silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate, etc.) on which the above positive photoresist composition is used for the production of precision integrated circuit devices. After applying a suitable coating method such as pre-baking, exposing through a predetermined mask, and if necessary post-heating (PEB: Post Exposure
A good resist can be obtained by performing Bake), developing, rinsing and drying. Examples of the present invention will be shown below, but the present invention is not limited thereto.
In addition,% indicates weight% unless otherwise specified.

[0072]

【Example】

Synthesis Example 1 188 g of phenol was placed in a reaction flask having a capacity of 500 ml, and heated to 80 ° C. to melt. To this, 1.42 g of BF ₃ · ethyl ether was added, 66 g of dicyclopentadiene was added dropwise over 3 hours with stirring, and the mixture was further heated at 100 ° C. for 2 hours.
The reaction was carried out for a time to obtain a modified phenol resin reaction solution. After the residual phenol was distilled off at 100 to 180 ° C. under reduced pressure, 550 g of toluene was added and dissolved. 800 for this
Then, ion-exchanged water (g) was added, and the mixture was shaken and washed. After the washing operation was performed 5 times or more, toluene and the like were distilled off at 100 to 180 ° C. under reduced pressure and then allowed to cool to obtain about 168 g of modified phenol resin A. The weight average molecular weight was 2020 and the softening point was 117 ° C.

Synthesis Example 2 188 g of phenol was placed in a reaction flask having a capacity of 500 ml and heated to 80 ° C. to melt. To this, 1.42 g of BF ₃ .ethyl ether was added, and 66 g of dicyclopentadiene was added dropwise over 3 hours with stirring. Then 35%
61.7 g of formaldehyde aqueous solution was added dropwise at 100 ° C. over 2 hours, and the reaction was continued for 1 hour to obtain a modified phenol resin reaction solution. After the residual phenol was distilled off at 100 to 180 ° C. under reduced pressure, 550 g of toluene was added and dissolved. To this, 900 g of ion-exchanged water was added and shaken and washed. After performing the washing operation 5 times or more, under reduced pressure 1
Toluene and the like were distilled off at 00 to 180 ° C. and allowed to cool to obtain about 220 g of modified phenol resin B. It had a weight average molecular weight of 2710 and a softening point of 118 ° C.

Synthesis Example 3 A weight-average molecular weight of 137 was placed in a reaction flask having a capacity of 500 ml.
186g of 0 dicyclopentadiene modified phenolic resin
Then, 58 g of phenol and 76 g of p-cresol were added, and the mixture was heated to 100 ° C. and melted. The subsequent treatment was carried out in the same manner as in Synthesis Example 2, and about 193 g of modified phenol resin C
Got The weight average molecular weight was 3720 and the softening point was 121 ° C.

Synthesis Example 4 A reaction flask having a capacity of 500 ml had a weight average molecular weight of 137.
186g of 0 dicyclopentadiene modified phenolic resin
Then, 106 g of m-cresol and 36 g of 3,5-dimethylphenol were added, and the mixture was heated to 100 ° C. and melted.
The subsequent treatment was performed in the same manner as in Synthesis Example 2 to obtain about 187 g of modified phenol resin D. Weight average molecular weight 2875,
The softening point was 127 ° C.

Synthesis Example 5 1489 g of o-cresol and 300 g of toluene were charged into a 5 liter reactor equipped with a reflux condenser and a Liebig condenser, heated to 170 ° C. and toluene 250 was added.
g was distilled off and dehydrated until the water content in the system reached 50 ppm. Then, the system was cooled to 80 ° C., 38 g of boron trifluoride-phenol complex was added, and 383 g of 4-vinylcyclohexene having a water concentration of 20 ppm was added over 1.5 hours while controlling the reaction temperature at 80 ° C. It was dripped slowly. After the dropping was completed, the reaction was continued at 80 ° C for 40 minutes, and then 1
The temperature was raised to 40 ° C., and the mixture was further heated and stirred for 2.5 hours.
After completion of the reaction, magnesium compound "KW-1000" (trade name:
After adding 89 g of Kyowa Chemical Industry Co., Ltd. and stirring for 60 minutes to inactivate the catalyst, the reaction solution was filtered using a filter paper covered with Celite. The resulting clear filtrate is 230
It was distilled under reduced pressure at 0 ° C. to obtain 550 g of modified phenol resin E. The weight average molecular weight was 2620 and the softening point was 106 ° C.

Synthesis Example 6 Synthesis of Photosensitive Material a 39.1 g of modified phenol resin A described in Synthesis Example 1,
53.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 800 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, 21.2 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 3 l of a 1% hydrochloric acid aqueous solution, the resulting precipitate was filtered off, washed with water and dried (40 ° C.), and 1,2-naphthoquinonediazide-5-sulfonate of modified phenol resin A (photosensitive) 69.6 g of the product a) was obtained.

Synthesis Examples 7 to 10 Synthesis of Photosensitive Materials b to e Photosensitive materials under the conditions shown in Table 1 in the same manner as in Synthesis Example 6 except that modified phenol resins B to E were used instead of the modified phenol resin A. be obtained.

Table 1: ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Modified phenol resin Yield type Weight (g) (g) ──── ──────────────────────── Photosensitive material b B 36.3 67.5 c C 38.1 64.2 d D 39.6 66.2 e E 39.3 65.1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Synthesis Example 11 Synthesis of Photosensitive Material f 2,3,4,4′-Tetrahydroxybenzophenone 1
2.3 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 40.3 g, and acetone 300 ml 3
It was charged in a single-necked flask and uniformly dissolved. Then, triethylamine / acetone = 15.2 g / 50 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. 1% of reaction mixture
It was poured into 1500 ml of hydrochloric acid aqueous solution, the precipitate formed was separated by filtration, washed with water and dried (40 ° C.), and then 2, 3, 4, 4′-
1,2-naphthoquinonediazide-5-sulfonic acid ester of tetrahydroxybenzophenone (photosensitive material f) 3
9.7 g was obtained.

Synthesis Example 12 Synthesis of Photosensitive Material g α, α, α′-Tris (4-hydroxyphenyl) -1
-Ethyl-4-isopropylbenzene 42.5 g, 1,
2-naphthoquinonediazide-5-sulfonyl chloride 6
1.8 g and 650 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 24.4 g / 80 ml was gradually added dropwise at 25 ° C.
And reacted for 4 hours. The reaction mixture is 1% aqueous hydrochloric acid solution 25
Pour into 00 ml, filter the resulting precipitate, wash with water and dry
(40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (photosensitive material g) 83. 1 g was obtained.

Synthesis Example 13 Synthesis of Photosensitive Material h 2,2-bis [4-hydroxy-3,5di (4-hydroxybenzyl) phenyl] propane 30.8 g, 1,2
-Naphthoquinonediazide-5-sulfonyl chloride 5
3.8 g and 600 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 21.3 g / 50 ml was gradually added dropwise at 25 ° C.
And reacted for 6 hours. The reaction mixture is 1% aqueous hydrochloric acid solution 25
Pour into 00 ml, filter the resulting precipitate, wash with water and dry
(40 ° C.) to give 2,2-bis [4-hydroxy-
67.2 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 3,5 di (4-hydroxybenzyl) phenyl] propane (photosensitive material h) was obtained.

Synthesis Example 14 Synthesis of Photosensitive Material i Tertiary butylphenol-formaldehyde resin (PR-50530 manufactured by Sumitomo Dures) 33.8 g,
53.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 800 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, 21.2 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 3 l of a 1% hydrochloric acid aqueous solution, the precipitate formed was separated by filtration, washed with water and dried (40 ° C.), and the tert-butylphenol-formaldehyde resin 1,
61.8 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material i) was obtained.

Synthesis Example 15 Synthesis of Novolac Resin A m-cresol 40 g, p-cresol 60 g, 37%
Formalin aqueous solution (49 g) and oxalic acid (0.13 g) were charged into a three-necked flask, heated to 100 ° C. with stirring, and reacted for 15 hours. Then raise the temperature to 200 ° C,
The pressure was gradually reduced to 5 mmHg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten alkali-soluble novolak resin was returned to room temperature and recovered. The obtained novolak resin A had a weight average molecular weight of 7100 (in terms of polystyrene).

Synthesis Example 16 Synthesis of Novolac Resin B m-cresol 50 g, p-cresol 25 g, 2,5
-Xylenol 28 g, 37% formalin aqueous solution 53 g
Further, 0.15 g of oxalic acid was charged into a three-necked flask, and the temperature was raised to 100 ° C. with stirring to react for 11 hours. Thereafter, the temperature was raised to 200 ° C., and the pressure was gradually reduced to 1 mmHg to distill off water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten novolak resin was returned to room temperature and recovered. The obtained novolak resin had a weight average molecular weight of 4,300 (in terms of polystyrene). Next, 20 g of this novolak resin was completely dissolved in 60 g of methanol, and then 30 g of water was gradually added thereto with stirring to precipitate the resin component. The upper layer was removed by decantation, the precipitated resin component was recovered, heated to 40 ° C., and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin B. The obtained novolak resin had a weight average molecular weight of 8920 (in terms of polystyrene), and the contents of the monomer, dimer and trimer were 0% and 2.3, respectively.
% And 3.5%. By the fractional reprecipitation operation, 47% of low molecular weight components were removed.

Synthesis Example 17 Synthesis of Novolac Resin C 60 g of m-cresol, 20 g of p-cresol, 2,
25 g of 3,5-trimethylphenol, 56 g of a 37% aqueous formalin solution and 0.16 g of oxalic acid were charged into a three-necked flask, and the temperature was raised to 100 ° C. with stirring to react for 16 hours. Then raise the temperature to 200 ° C and gradually increase to 1
The pressure was reduced to mmHg, and water, unreacted monomers, formaldehyde, oxalic acid, etc. were distilled off. Then, the molten novolak resin was returned to room temperature and recovered. The obtained novolak resin had a weight average molecular weight of 3800 (in terms of polystyrene). Then, 20 g of this novolak resin was completely dissolved in 60 g of acetone, and then 60 g of hexane was added thereto.
Was slowly added with stirring, and the mixture was allowed to stand for 2 hours, the upper layer was removed by decantation, and the precipitated resin component was recovered, heated to 40 ° C., and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin C. Obtained. The obtained novolak resin has a weight average molecular weight of 8300 (converted to polystyrene).
And the dispersity was 3.20. Also, the monomer,
The contents of dimer and trimer are 0%, 2.1%,
It was 3.0%. By the fractional reprecipitation operation, 56% of low molecular weight components were removed.

Synthesis Example 18 Synthesis of Novolac Resin D 30 g of p-cresol, 14 g of o-cresol, 2,3
-Dimethylphenol 50g, 2,3,5-trimethylphenol 20g, 2,6-dimethylphenol 4.9
g was mixed with 50 g of diethylene glycol monomethyl ether and equipped with a stirrer, a reflux condenser and a thermometer.
I put it in a one-necked flask. Next, 85 g of a 37% formalin aqueous solution was added, and the mixture was stirred while heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 6.3 g of oxalic acid 2
The hydrate was added. Then, the temperature of the oil bath is adjusted to 13 for 18 hours.
The reaction was continued at 0 ° C, the reflux condenser was removed, and the mixture was distilled off under reduced pressure at 200 ° C to remove unreacted monomers. The obtained novolak resin has a weight average molecular weight of 328.
It was 0 (polystyrene conversion) and the dispersity was 2.75.

Preparation and Evaluation of Positive Photoresist Composition Photosensitive materials a to i obtained in the above Synthesis Examples 6 to 14, novolak resins A to D obtained in the above Synthesis Examples 15 to 18, a solvent and, if necessary, The polyhydroxy compounds were mixed in the proportions shown in Table 2 to form a uniform solution, which was then filtered using a Teflon microfilter having a pore size of 0.10 μm to prepare a photoresist composition. This photoresist composition was applied onto a silicon wafer using a spinner while changing the rotation speed, and dried at 90 ° C. for 60 seconds on a vacuum adsorption type hot plate to obtain resists having film thicknesses of 0.97 μm and 1.02 μm, respectively. A film was obtained. This film was exposed using a reduction projection exposure device (reduction projection exposure device NSR-2005i9C manufactured by Nikon Corporation), and then PEB was performed at 110 ° C. for 60 seconds to 2.3.
It was developed with an 8% tetramethylammonium hydroxide aqueous solution for 1 minute, washed with water for 30 seconds and dried. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. The results are shown in Table 3. The sensitivity was defined as the reciprocal of the exposure dose for reproducing a mask pattern of 0.60 μm, and shown as a relative value with respect to the sensitivity of Comparative Example 1 at a resist film thickness of 1.02 μm. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.60 μm. The heat resistance was a temperature at which a resist-patterned silicon wafer was baked on a hot plate for 4 minutes and the deformation of the pattern did not occur. Resist shape is 0.50 μm
The angle (θ) formed by the resist wall surface and the plane of the silicon wafer in the cross section of the resist pattern is shown. The development residue was examined by observing a patterned silicon wafer with a scanning electron microscope. The one in which the residue was not observed was represented by ◯, and the one in which the residue was observed was represented by x. Regarding the storage stability, the solution of the positive photoresist composition was allowed to stand at room temperature, and the presence or absence of precipitates in the solution was examined after 6 months. The thing which precipitation was not observed was represented by (circle), and the thing observed was represented by x.

Table 2: Formulation of positive photoresist composition ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Novolak resin Photosensitive material Polychtoxyl compound ^{* 1} Solvent ^{* 2} Addition amount type Addition amount type Addition amount type Addition amount ─────────────────────────── ────────── Example 1 A100a27-S-13502A100b27-S-13803A100c28-S-33604B81a28 P-1 19 S-2 / S-4 285/95 5 B 79 b 32 P-2 21 S-1 380 6 B 80 d 30 P-3 20 S-2 380 7 B 82 e 27 P-2 18 S -3 360 8 B 77 a / g 16/16 P-3 23 S-2 380 9 C 79 a / h 17/13 P-1 21 S-2 370 10 81 c 27 P-3 19 S-2 / S-4 285/95 11 C 78 b 31 P-1 22 S-1 340 12 D 82 a 30 P-2 18 S-1 340 13 D 86 b 28 P- 3 14 S-1 340 14 D 86 c 29 P-1 14 S-2 370 ───────────────────────────────── Comparative Example 1 A 100 f 27 − − S-1 3502 A 100 g 27 − − S-1 350 3 A 100 h 26 − − S-2 380 4 A 100 i 28 − − S-2 380 5 A 95 g 29 P-4 5 S-2 380 6 B 79 g 31 P-1 21 S-2 370 7 B 79 h 31 P-3 21 S-2 380 8 C 78 i 29 P-2 22 S. -1 350 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ * 1 P-1: α, α, α'-tris (4-human benzyloxyphenyl) -1-ethyl-4-isoprophylbenzene P-2: Tris (4-human oxyphenyl) methane P-3: 1,1- Bise (4-human oxyphenyl) cyclohexane P-4: modified phenolic resin A * 2 obtained in Synthesis Example 1 S-1: ethyl cellosolve acetate S-2: 2-human ethyl ethoxypropionate S-3: 3-methoxypropionic acid Methyl S-4: 3-Ethoxypropionate ethyl

[0090]

[Table 1]

[0091]

The positive photoresist using the photosensitive material of the present invention is excellent in sensitivity and resolution, and particularly, the performance is less dependent on the film thickness, and the development residue and the storage stability are excellent.

Claims (1)

[Claims] 1. A 1,2-naphthoquinonediazide-5- (and / or -4) of an alkali-soluble resin and a polyhydroxy compound having a structure represented by the following general formula (I):
-) A positive photoresist composition containing a sulfonic acid ester. [Chemical 1] Here, Y: —SO ₂ — or —SO ₂ —Z—SO ₂ —, Z: alkylene group, R ₁ , R ₂ : may be the same or different, and may be a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or alkoxy. Group, R _{3 to} R ₆ : may be the same or different, and represent a hydrogen atom, an alkyl group or an aryl group, m, n, o, m ′, n ′: an integer of 1 to 3.