KR100535903B1 - Positive Photoresist Composition - Google Patents

Abstract

(Problem) The vibration width (swing width) of the line width with respect to the fluctuation of the film thickness is small, and has high resolution, and also the halftone phase difference shift mask aptitude (sidelobe light tolerance) which was not compatible conventionally is good, and there is little development defect, Providing a positive photoresist composition with few residual standing waves and excellent resist performance.

(Solution) As an alkali-soluble resin, an alkali-soluble low molecular compound, a quinone diazide sulfonic acid ester photosensitive agent, the diester of the quinone diazide of the phenolic low molecular weight compound of a specific structure, and the full ester of the quinone diazide of a specific structure is mentioned. Positive photoresist composition each containing in specific content.

Description

Positive photoresist composition

The present invention relates to a positive photoresist composition for microfabrication such as a semiconductor device containing an alkali-soluble resin and a specific quinonediazidesulfonic acid ester, and which is sensitive to radiation such as ultraviolet rays and far ultraviolet rays, and more particularly, variations in film thickness. The present invention relates to a positive photoresist composition having a narrow oscillation width with a high resolution, high resolution, good halftone retardation shift mask, low development coupling, low standing waves, and excellent resist performance.

The positive photoresist is applied on a substrate such as a semiconductor wafer, glass, ceramics or metal with a thickness of 0.5 to 2 탆 by the spin coating method or the roller coating method. Thereafter, the substrate is heated and dried, and the circuit pattern or the like is baked by ultraviolet irradiation or the like through an exposure mask, and developed by performing post-exposure bake as necessary to form a positive image.

In addition, the pattern development can be processed on the substrate by etching the positive image as a mask. Typical applications include semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

Generally as a positive photoresist composition, the composition containing alkali-soluble resin binders, such as novolak, and the naphthoquinone diazide compound as a photosensitive material is used.

The novolak resin as a binder is particularly useful in the present application because it is soluble in an alkaline aqueous solution without swelling, and when the resulting image is used as a mask for etching, it is particularly resistant to plasma etching. In addition, the naphthoquinone diazide compound used as a photosensitive agent acts as a dissolution inhibiting agent which lowers the alkali solubility of the novolak resin itself, but when it is decomposed under light irradiation, an alkali soluble substance is generated and rather the alkali of the novolak resin It is unique in that it acts to increase solubility, and is particularly useful as a photosensitive material of positive photoresist because of its large property change for light.

Until now, many positive photoresists containing novolak resins and naphthoquinone diazide-based photosensitive materials have been developed and put into practical use. In particular, advances in resist materials toward high resolution are surprising, and sufficient results have been obtained in line width processing down to submicron.

Conventionally, in order to increase the resolution and obtain a good pattern shape, the use of a resist having a high contrast (γ value) is advantageous, and the technical development of a resist composition suitable for this purpose has been performed. There are a very large number of publications that disclose these techniques. In particular, for the novolak resin which is the main part of the positive photoresist, many patent applications have been filed regarding the monomer composition, the molecular weight distribution, the synthesis method, and the like, and a certain result has been obtained. In addition, many compounds having a structure effective for high contrast have also been disclosed with respect to a photosensitive material which is another main component. By designing a positive photoresist using these techniques, it is also possible to develop an ultra high resolution resist capable of resolving a dimensional pattern approximately equal to the wavelength of light.

In addition, integrated circuits are gradually increasing in density, and in the manufacture of semiconductor substrates such as ultra-LSIs, an ultra-fine pattern consisting of a line width of 0.5 µm or less is required.

In the formation of an ultrafine pattern such as 0.5 µm or less, it has been found that even if a certain resolution is obtained, for example, at a certain coating film thickness, there is a phenomenon in which the oscillation width (swing width) of the line width obtained increases when the coating film thickness varies. . In practice, when processing a semiconductor substrate, a pattern is formed by using a resist film coated with a slightly different film thickness at each place due to irregularities in the substrate surface and unevenness of the coating film thickness. Therefore, when performing micromachining close to the resolution limit using a positive photoresist, the abnormality of the swing width according to the film thickness variation became one obstacle.

Until now, many 1, 2- naphthoquinone diazide compounds of the polyhydroxy compound which have a specific structure are proposed in order to raise resolution. On the other hand, the use of the photosensitive material which has a hydroxyl group in a molecule | numerator has also been proposed in many cases by which the resist which has high contrast and high resolution is obtained.

However, the photosensitive material which has a hydroxyl group in the conventional molecule becomes more demanded by the high integration of a semiconductor, etc., and is not fully satisfied.

On the other hand, various tests have been made to further increase the resolution by super-resolution techniques such as an exposure technique or a mask technique. In the super resolution technology, various super resolution technologies have been studied on the light source surface, the mask surface, the pupil surface, and the upper surface, respectively. On the light source surface, it is a technique which raises the resolving power by making into a shape different from the conventional circular shape, ie, the conventional illumination source. On the mask surface, the technique which obtained the high resolution by controlling the phase also using a phase shift mask, ie, adding a phase difference to the light which permeate | transmits a mask and using the interference as desired has been reported. (For example, Itoudoku Hisa: Optical (1) to (4) of stepper, phototechnical contact, Vol. 27, No. 12, 762 (1988), Vol. 28, No. 1, 59 (1990), Vol. 28, No. 2, 108 (1990), Vol, 28, No. 3,165 (1990), Japanese Patent Laid-Open No. 58-173744, Japanese Patent No. 62-50811, Japanese Patent Publication No. 62-67514, Japanese Patent Application Laid-Open No. 1-47458, Appears 1-283925, East 2-211451, etc.)

Moreover, although the resist exposure method using the halftone system phase shift mask as described in Unexamined-Japanese-Patent No. 8-15851 has attracted particular attention as a practical technique which improves the spatial image and contrast of a projection image, it is a resist. In the light intensity distribution of the exposure light reaching to, a so-called sub-peak different from the main peak is generated, and the portion of the resist which should not be originally exposed is exposed. In particular, the higher the interference sigma, the larger the sub-peak. When such a sub peak occurs, unevenness due to the sub peak is formed in the resist after exposure and development in the positive resist, which is not preferable.

In the projection optical system of the photolithography, various miniaturization studies have been conducted, and a combination of various super resolution techniques has also been studied (for example, a halftone phase shift mask and an annular rough surface: CNAhn et al; SPIE, Vol. 2440, 22 (1995), T. Ogawa et al; SPIE, Vol. 2726, 34 (1996)).

However, when the super-resolution technique is applied, conventional positive photoresists have been reported to have a low resolution, insufficient exposure margin, insufficient exposure latitude, unevenness (film reduction), and deterioration of resist performance. It is done. For example, CLLins have reported that deformity illumination degrades the roughness of patterns due to the effect of optical proximity (SPIE, Vol. 2726, 437 (1996), and N. Samarakone and IBHurs). When forming a contact hole pattern using a tone phase shift mask, it is pointed out that the periphery of the hole pattern is uneven due to the influence of side lobe light (SPIE, Vol. 2440, 61 (1995), SPIE, Vol. 2440,278 (1995)).

In order to reduce the effects of side lobe light, studies have been carried out on surface treatment of positive photoresists with alkali after exposure (T. Yasuzato etal; SPIE, Vol. 2440,804 (1995)), but the process is complicated. There is a problem.

In addition, Japanese Patent Laid-Open No. 2-103543 discloses the use of a quinonediazide complete ester and a diester of a polyhydroxy compound having a specific structure as a photosensitizer. Japanese Patent Laid-Open No. Hei 6-202321 discloses the use of a photosensitizer containing 40% or more of quinonediazidesulfonic acid diesters of compounds having three or more phenolic hydroxyl groups. In addition, JP-A-8-99952 discloses using a quinone diazide ester body having a specific structure as a photosensitive agent. However, even in the positive photoresist composition using these photosensitizers, the swing width due to the variation in film thickness is large, the development defect and the number of residual standing waves are large, the halftone mask exposure aptitude is insufficient, and none of these qualities are satisfied. .

As described above, when the super resolution technique is used, resolution is improved, but other resist performances may be lowered. Therefore, when using a super resolution technique, it is rarely known in the art whether a positive photoresist material should be designed separately, for example.

Accordingly, an object of the present invention is to produce a semiconductor device and the like, in which the oscillation width (swing width) of the line width with respect to the variation in the film thickness is small, which has a high resolution and a conventionally compatible halftone phase shift shift mask aptitude (side It is an object of the present invention to provide a positive photoresist composition having good lobe resistance, low development defects, low residual standing waves, and excellent resist performance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining all the said characteristics, the said subject is solved by the quinonediazide sulfonic-acid ester photosensitive agent containing a specific quinonediazide ester and a specific quinonediazide complete ester in the range of a specific mixing ratio. To the present invention.

That is, the object of the present invention can be achieved by the following configuration.

(1) A positive photoresist composition containing an alkali soluble resin, a quinone diazide sulfonic acid ester photosensitive agent and an alkali soluble low molecular compound, wherein the quinone diazide sulfonic acid ester photosensitive agent is

(A) The diester body of the quinone diazide of the phenolic low molecular compound which has 3-6 phenolic hydroxyl groups represented by following General formula [I], and

(B) contains the complete ester of quinone diazide represented by the following general formula [II] or [III-1]-[III-3],

The area ratio of the pattern area of the diester body of the above-mentioned (A) to the total pattern area of the photosensitive agent is 25% or more and less than 50% in a specific high-speed liquid chromatography using a detector using ultraviolet rays of 254 nm, and the (B) The area ratio of the complete ester of this is 3% or more and 60% or less, The positive photoresist composition characterized by the above-mentioned.

General formula [1]

(R ₁ ~R _4: may be the same and different and each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group,

R <_5> , R <_{6> may be} same or different, and represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, and an aryl group, and when m is two or more, it is the case of several R <_5> or R <_6> Each may be same or different,

R ₇ : represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, and when m is 2 or more, each of the plurality of R ₇ may be the same or different;

A; They may be the same or different and are a single bond, -O-, -S-, -SO-, -SO _2- , -CO-, -CO _2- , -C (R ₈ ) (R ₉ )-,- A group of N (R ₁₀ )-, -N (R ₁₀ ) SO ₂ -or a combination of a plurality thereof, and

R ₈ and R _{9 may be the} same or different, may represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ₈ and R ₉ may be bonded to each other to form a cycloalkyl group,

R ₁₀ : represents a hydrogen atom, an alkyl group,

m: integer of 1-4)

General formula [II]

(R ₁₁ to R ₁₂ : which may be the same or above, -OQ (Q represents a naphthoquinone diazide-5- (and / or -4-) sulfonyl group described below),

R <_13> -R <_{17> may be} same or above and may be a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, an acyloxy group, a halogen, a nitro group, and a cyano group , A cyclohexyl group or -OQ (Q is the same as above),

R ₁₈ to R _{21 may be the} same or different and represent an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyloxy group or a cyclohexyl group.

However, in General Formula (II), the number of Q is two or more and less than six.)

General formula [III-1]-[III-3]

(Q: same as above,

R _{22 may be the} same or different and represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or an acyloxy group,

R <_{23> may be} same or different, and represents a hydrogen atom and an alkyl group,

x: represents the integer of 1-3,

y: represents the integer of 1-6.)

(2) The positive photoresist composition according to the above (1), wherein an area ratio of the diester body pattern area to the total pattern area is 25% or more and less than 40%.

In accordance with the above-described configuration, the present invention has a positive vibration width of the line width, high resolution, good halftone retardation shift mask, good development defects, little standing waves, and excellent resist performance. A photoresist composition could be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The phenolic low molecular weight compound represented by general formula [I] is demonstrated. In R ₁ to R ₄ of the general formula [I], as the halogen atom, a chlorine atom, a bromine atom or an iodine atom is used as the alkyl group, and a methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group or The cycloalkyl group is preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group as the cycloalkyl group, such as a t-butyl group. As an alkenyl group, a C2-C4 alkenyl group like a vinyl group, a propenyl group, an allyl group, or butenyl group is preferable. The alkoxy group has 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, isobutoxy group, sec-butoxy group or t-butoxy group. Alkoxy groups are preferred. As an aryl group, a phenyl group, xylyl group, toluyl group, cumenyl group, and an acyl group are preferable formyl group, acetyl group, butyryl group, benzoyl group, cyanamoyl group, and valeyl group.

In R <_5> , R <_6> , R < ₇ > of the said General formula [I], as a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, and an aryl group, the halogen atom, alkyl group, described in said R <_1> -R <_4> , The same thing as a cycloalkyl group, an alkenyl group, an alkoxy group, and an aryl group is preferable.

In R <_8> , R < ₉ > of the said General formula [I], as an alkyl group, an aryl group, a halogen atom, and the cycloalkyl group couple | bonded with each other, the thing similar to the alkyl group, aryl group, and halogen atom cycloalkyl group described in said R <_1> -R <_4> is the same. desirable.

In R ₁₀ , the alkyl group is preferably the same as the alkyl group described for the above R ₁ to R ₄ .

As a specific example of the phenolic low molecular weight compound represented by General formula [1], the compound etc. which are represented by following [I-1]-[I-69] are mentioned. However, these do not limit the content of the present invention. These phenolic low molecular weight compounds are used individually or in combination of 2 or more types.

In this invention, at least 1 sort (s) of the compound represented by said general formula [II] and [III-1]-[III-3] is used as quinonediazide complete ester.

In general formula [II], in R <_13> -R <_21> , Preferably, a C1-C12 alkyl group or an alkoxy group, a C6-C15 aryl group, aryloxy group aralkyl group, or aralkyloxy group, C2-C15 An aliphatic acyl group, an aromatic acyl group, an acyloxy group, a halogen, a nitro group, a cyano group, or a -OQ group.

Preferable specific examples of the alkyl group, the alkoxy group, the aryl group, the acyl group and the halogen include the same as those represented by the general formula [I].

Specific examples of the aryloxy group include phenoxy group, toluyloxy group, xylyloxy group, mesityloxy group, methoxyphenyloxy group and the like.

As a specific example of an aralkyl group, a benzyl group, toluylmethyl group, xylylmethyl group, etc. are mentioned. Specific examples of the aralkyloxy group include benzyloxy group, toluylmethyloxy group, xylylmethyloxy group and the like.

In the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group or aralkyloxy group, alkoxy group, aryloxy group, aryl group, hydroxyl group, carboxyl group, sulfonic acid group, amino group, nitro group, silyl group as a substituent It may further have a silyl ether group, a cyano group, an aldehyde group, a mercapto group or a halogen atom.

As a specific example of the quinonediazide complete ester body represented by general formula [II], the compound etc. which are represented by following [II-1]-[II-8] are mentioned. However, these do not limit the content of the present invention.

In the general formulas [III-1] to [III-3], for R ₂₂ , a chlorine atom, a bromine atom or an iodine atom as a halogen atom and a methyl group, ethyl group, propyl group, n-butyl group or isobutyl group as an alkyl group As a cycloalkyl group, a C1-C4 alkyl group, such as a sec-butyl group or t-butyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable. As an alkenyl group, a C2-C4 alkenyl group like a vinyl group, a propenyl group, an allyl group, or butenyl group is preferable. As an aryl group, a phenyl group, xylyl group, toluyl group, cumenyl group, an aralkyl group is a C6-C15 thing, an alkoxy group is a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group And an alkoxy group having 1 to 4 carbon atoms such as isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group is preferable. As the acyl group, a formyl group, an acetyl group, a butyryl group, a benzoyl group, a cyanamoyl group and a valeryl group are preferable.

As an alkoxycarbonyl group, a benzoyloxy group is preferable and as an acyloxy group, a butyryloxy group and an acetoxy group are preferable.

In R ₂₃ , the alkyl group is preferably the same as the alkyl group described in R ₂₂ .

As a specific example of the quinonediazide complete ester body represented by general formula [III-1]-[III-3], the compound etc. which are represented by following [III-1-1]-[III-3-12] are mentioned. . However, these do not limit the content of the present invention.

A characteristic of the compound of the general formula [I] is that the reaction with quinonediazidesulfonyl chloride at the time of introducing three to six aromatic rings linearly, having one hydroxyl group in each aromatic ring, and introducing a photosensitive group It is a structure which is easy to advance to the hydroxyl group on the terminal aromatic ring.

The method for synthesizing a phenolic low molecular compound represented by the general formula [I] can generally be obtained by methylolation reaction of a phenol compound and dehydration condensation reaction of a produced methylol body and a phenol compound. For example, the method described in Unexamined-Japanese-Patent No. 5-323597, Unexamined-Japanese-Patent No. 7-261382, etc. can be used.

The characteristic of the compound of the general formula [II] is the number of aromatic rings, the linking direction thereof, and the number of quinonediazidesulfonyl groups. The number of quinonediazidesulfonyl groups is preferably 2 to 4, with 3 being most preferred. The synthesis method of general formula [II] is generally obtained by making aromatic aldehydes and phenols react on acid catalyst conditions, and the method of Unexamined-Japanese-Patent No. 4-328555 can be used.

The structural features of the compounds of the general formulas [III-1] to [III-3] are the number of aromatic rings and the number of quinonediazidesulfonyl groups as described above. The synthesis method is obtained by the reaction of a terpene compound and a phenol compound, and the method described in JP-A-9-106070 can be used.

In the present invention, the photosensitive agent is a polyhydroxy compound before the esterification reaction of the phenolic low molecular compound represented by the general formula [I] and the photosensitive agent of the general formula [II] and [III-1] to [III-3]. A part or all of the hydroxyl group of is obtained by performing general esterification reaction in the presence of 1,2-naphthoquinone diazide-5- (and / or -4-) sulfonyl chloride and a basic catalyst. .

That is, a predetermined amount of phenolic low molecular compound, 1,2-naphthoquinone diazide-5- (and / or -4-) sulfonyl chloride, a solvent, for example dioxane, acetone methyl ethyl ketone N Methylpyrrolidone, dimethoxyethane, tetrahydrofuran, diglyme, ethyl acetate, dichloroethane, chloroform, γ-butyrolactone and the like are placed in a flask, and a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate , Triethylamine, 4-dimethylaminopyridine, N-methylmorpholine, N-methylpiperidine, N-methylpyrrolidine and the like are added dropwise and condensed. The obtained product is purified after washing with water and dried.

In general esterification, other mixtures varying in esterification number and esterification position are obtained, but only certain specific isomers may be selectively esterified by selecting the synthetic conditions or the structure of the phenolic low molecular weight compound. The esterification rate as used in the present invention is defined as the average value of this mixture.

The esterification rate thus defined can be controlled by the mixing ratio of the raw polyhydroxy compound (phenolic low molecular weight compound) and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride. Can be. In other words, the added 1,2-naphthoquinone diazide-5- (and / or -4-) sulfonyl chloride causes esterification in virtually all, so that in order to obtain a mixture of a desired esterification rate, What is necessary is just to adjust the molar ratio of a raw material.

As necessary, 1,2-naphthoquinone diazide-5-sulfonic acid ester and 1,2-naphthoquinone diazide-4-sulfonic acid ester can be used together. In addition, in the said method, reaction temperature is generally -20-60 degreeC, Preferably it is 0-40 degreeC.

As a photosensitizer of this invention, (A) diester body of quinonediazide of the phenolic low molecular weight compound represented by the said General formula [I], and (B) following General formula [II] or [III-1]-[III-3] The complete ester of quinonediazide represented by] is contained in a specific ratio. It is preferable that the ratio of the diester of the said (A) in all the photosensitive objects is 25% or more and less than 50% as an area ratio with respect to the whole pattern area of the photosensitive agent in high-speed liquid chromatography which makes 254 nm ultraviolet-rays a measurement wavelength, More preferably, it is 25% or more and less than 40%, More preferably, it is 28% or more and 38% or less.

If the resolution is lower than 25%, problems such as an increase in development defects or a change in film thickness, which are effects of the present invention, and a change in film thickness become large, and standing waves also increase. Shift mask aptitude deteriorates and becomes a problem.

It is preferable that the ratio of the complete ester of said (B) is 3% or more and 60% or less as an area ratio with respect to the whole pattern area of a photosensitive agent in the same high-performance liquid chromatography as mentioned above, More preferably, it is 4% or more and 50%. It is below, More preferably, it is 5% or more and 40% or less. If it is less than 3%, halftone retardation shift mask aptitude deteriorates, and if it exceeds 60%, there is a problem such as an increase in development defects or a change in line width due to film thickness variation, and standing waves also increase.

When using the photosensitive compound (photosensitive agent) of this invention synthesize | combined by the above method as a resin composition, the diester body of quinonediazide of the phenolic low molecular weight compound of the said General formula [I], and [II] or [III] Specific amounts of the complete ester of quinone diazide represented by -1] to [III-3] are mixed, and the mixture is blended and used in alkali-soluble resin, but the blending amount is described above with respect to 100 parts by weight of novolak resin. 10 to 120 parts by weight of the mixture, preferably 15 to 90 parts by weight. When the use ratio is less than 10 parts by weight, the residual film rate is remarkably reduced, and when it exceeds 120 parts by weight, the sensitivity and solubility in a solvent decrease.

Examples of the alkali-soluble resin used in the present invention include novolak resins, acetone pyrrologalol resins, polyhydroxystyrenes and derivatives thereof.

Of these, novolak resins are particularly preferred, and the resulting monomers are obtained by addition condensation with aldehydes in the presence of an acidic catalyst as a main component.

Predetermined monomers include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3- Alkylphenols, such as xylenol, such as xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, and pt-butylphenol, 2,3,5-trimethylphenol, 2,3,4-trimethylphenol Trialkylphenols such as p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol and m- Alkoxyphenols such as propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol and p-chlorophenol Although hydroxy aromatic compounds, such as o-chlorophenol, dihydroxy phenol, bisphenol A, phenol phenol, resorcinol, and naphthol, can be used individually or in mixture of 2 or more types, it is not limited to these.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetoaldehyde, propylaldehyde, benzaldehyde, phenylacetoaldehyde, 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-hydroxybenzaldehyde , p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacenoaldehyde and acetals thereof, such as chloroacetoaldehyde diethyl acetal, can be used, but among these, formaldehyde is preferably used.

These aldehydes are used individually or in combination of 2 or more types. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

In addition, Japanese Patent Laid-Open Nos. 60-45238, 60-97347, 60-140235, 60-189739, 64-14229, Japanese Patent Laid-Open Nos. 1-276131, 2-2615, 2-275955, 2 -282745, 4-101147, 4-122938 and the like, for example, to remove or reduce the low-molecular component of the novolak resin by a method such as fractional precipitation, fractional dissolution, column chromatography, etc. It is preferable to use one.

It is preferable that the weight average molecular weight of the novolak resin obtained in this way is 1500-15000. If it is less than 1500, the film | membrane reduction after image development of an unexposed part is large, and when it exceeds 25000, the image development speed will become small. Here, the weight average molecular weight is defined with the polystyrene conversion value of gel permeation chromatography.

Moreover, the dispersion degree (ratio of weight average molecular weight Mw and number average molecular weight Mn, ie, Mw / Mn) of novolak resin is preferably 1.5 to 7.0, more preferably 1.5 to 5.0. When dispersion degree exceeds 7, it becomes difficult to obtain the effect of this invention. If the degree of dispersion is less than 1.5, since a high purification process is required when synthesizing the novolak resin, practical practicality is insufficient and is inappropriate.

The weight average molecular weight and the degree of dispersion of the novolak resin may be appropriately set according to the type of the novolak resin.

In the case of the novolak resin synthesized by the condensation reaction of the aldehyde compound with a mixture containing at least two kinds of phenol, cresol, xylenol and trimethyl phenol (but m-cresol is essential), The weight average molecular weight is preferably 5500 to 25000, and more preferably 6000 to 25000. In addition, the novolak resin preferably has a ratio (dispersion degree) of weight average molecular weight and number average molecular weight of 1.5 to 5.0.

The alkali-soluble resin is a mixture and aldehyde containing at least four of p-cresol, o-cresol, 2,3-xylenol, 2,6-xylenol and trimethylphenol (requires o-cresol). In the case of at least one novolak resin synthesized by the condensation reaction of the compound, the ratio of the weight average molecular weight and the number average molecular weight is 1.5 to 5.0, and the weight average molecular weight is preferably 1500 to 6000.

As mentioned above, the effect of this invention becomes more remarkable by setting weight average molecular weight and dispersion degree to a predetermined range according to the kind of novolak resin to be used.

As addition amount of alkali-soluble resin in the composition of this invention, 30-90 weight% is preferable with respect to the total solid in a composition, More preferably, it is 40-80 weight%.

In the present invention, the above photosensitizer can be mainly used, but, if necessary, esterified product of 1,2-naphthoquinone diazide-5- (and / or -4-) sulfonyl chloride of the polyhydroxy compound shown below. It can be used together in the range from which the effect of this invention is acquired.

Examples of the polyhydroxy compound include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-tri Hydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,6,3', 4'-pentahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 5'-pentahydroxybenzophenone, 2,4,6 Polyhydroxybenzophenones such as 3'4 ', 5'-hexahydroxybenzophenone and 2,3,4,3'4', 5'-hexahydroxybenzophenone;

Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetphenone, 2,3,4-trihydroxypentyl ketone, and 2,3,4-trihydroxyphenylhexyl ketone,

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

Polyhydroxy benzoic acid esters such as 3,4,5-trihydroxybenzoic acid propyl, 2,3,4-trihydroxybenzoic acid phenyl, and 3,4,5-trihydroxybenzoic acid phenyl;

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

Alkylene-di (polyhydroxybenzoates) such as ethylene glycol-di (3,5-dihydroxybenzoate) and ethylene glycol-di (3,4,5-trihydroxybenzoate);

2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3 ', 5'-biphenyltetrol, 2,4,2', 4'-biphenylte Troll, 2,4,6,3 ', 5'-biphenylpentol, 2,4,6,2', 4 ', 6'-biphenylhexole, 2,3,4,2', 3 ', 4 Polyhydroxy biphenyls such as' -biphenyl hexol,

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'-tetrahydroxydiphenyl sulfoxide,

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

4,4 ', 3 ", 4" -tetrahydroxy-3,5,3', 5'-tetramethyltrienylmethane, 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 Polyhydroxytriphenylmethanes such as -5,5'-dipropionyltriphenylmethane,

3,3,3 ', 3'-tetramethyl-1,1'-spirobi-indane-5,6,5', 6'-tetrol, 3,3,3 ', 3'-tetramethyl-1 , 1'-spirobi-indane-5,6,7,5 ', 6', 7'-hexole, 3,3,3 ', 3'-tetramethyl-1,1'-spirobi-indane-4 , 5,6,4 ', 5', 6'-hexol, 3,3,3 ', 3'-tetramethyl-1,1'-spirobi-indan-4,5,6,5', 6 ' Polyhydroxyspirobi phosphates such as, 7'-hexole,

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], flavone pigments such as moline, quercetin, 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-din-propyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ', α "-tris (3,5-diisopropyl-4-hydrate Hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ', α "-tris (3,5-din-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-hydroxy Phenyl) 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'-hydroxy 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- [a ', alpha'-bis (4 "-hydroxyphenyl) ethyl] benzene, and the like.

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-brombenzoyl) 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-trihydrate Oxybenzoyl) 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-trihydroxyphenol, 4,6-bis- (2', 4 ', 6-trihydroxy-benzyl) -2,4-dimethyl Phenol, 4,6-bis- (2 ', 3', 4'-trihydroxy-benzyl) -2,5-dimethyl-phenol It can be given.

Moreover, the low nucleus body of phenol resins, such as a novolak resin, can be used.

The naphthoquinone diazide ester photosensitizer of these polyhydroxy compounds can be used individually or in combination of 2 or more types.

The said photosensitive agent which can be used together with the photosensitive material of this invention can be mix | blended in the ratio of 50 weight part or less normally, Preferably it is 30 weight part or less with respect to 100 weight part of photosensitive materials of this invention.

As an alkali-soluble low molecular weight compound which can be used for this invention, the low molecular weight compound which is water insoluble and has a phenolic hydroxyl group is mentioned.

Specifically as a water-insoluble alkali-soluble low molecular compound, a polyhydroxy compound is mentioned.

Preferred polyhydroxy compounds include phenols, resorcin, fluoroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, acetone-pyrrogalol condensation resin, chlorogluside, 2,4,2 ', 4'-biphenylterol, 4,4'-thiobis (1, 3-dihydroxy) benzene, 2,2 ', 4,4'-tetrahydroxydiphenylether, 2,2', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2 ', 4, 4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 '-(α-methylbenzylidene) bisphenol, α , α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α', α" -tris (4-hydroxyphenyl) -1-ethyl-4- Isopropylbenzene, 1,2,2-tris (hydroxyphenyl) propane, 1,2,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyfe Nil) ethane, 1,1, 3-tris (hydroxyphenyl) butane, para [(alpha), (alpha), (alpha) ', (alpha) "-tetrakis (4-hydroxyphenyl)]-xylene, etc. are mentioned.

Among these, as a water-insoluble alkali-soluble low molecular compound, the water-insoluble alkali-soluble low molecular compound which has a total carbon number of 60 or less in 1 molecule and has 2-8 phenolic hydroxyl groups in 1 molecule is preferable.

The water-insoluble alkali-soluble low molecular compound has a ratio of phenolic hydroxyl groups and aromatic rings of 0.5 to 1.4, and has at least one species having 12 to 60 carbon atoms in one molecule and 2 to 10 phenolic hydroxyl groups in one molecule. It is preferable that it is a water-insoluble alkali-soluble low molecular compound. Among these compounds, compounds which increase the alkali dissolution rate of the alkali-soluble resin when added to the water-insoluble alkali-soluble resin are particularly preferred. These improve the development latitude further.

Moreover, when the carbon number of the said compound is larger than 60, the effect of the addition is hard to express. In addition, if it is less than 12, new defects such as deterioration in heat resistance occur. In order to exert the addition effect, it is necessary to have at least two hydroxyl groups in the molecule, but when they exceed 10, the improvement effect of developing latitude is lost. Moreover, when the ratio of a phenolic hydroxyl group and an aromatic ring is less than 0.5, there exists a tendency for the film thickness dependence to become large, and developing latitude narrows. When this ratio exceeds 1.4, the stability of the composition is deteriorated, and it is difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The addition amount of this low molecular weight compound is 1 to 100 weight% with respect to alkali-soluble resin, More preferably, it is 2 to 80 weight%. The addition amount exceeding 100% by weight is not preferable because the development residue deteriorates, and a new defect that the pattern deforms during development occurs.

Examples of the water-insoluble alkali-soluble low molecular compound having an aromatic hydroxyl group to be used in the present invention include, for example, Japanese Patent Application Laid-Open No. 4-122938, East 2-28531, East 2-242973, East 2-275995, East 4-251849, East 5-303199, 5-244-, 66-301204, can be easily synthesized by those skilled in the art with reference to the methods described in each of Japanese Patent Nos. 4916210, 5210657, 5318875, and EP 219294 and the like. .

As a solvent which melt | dissolves the photosensitive material, alkali-soluble low molecular weight compound, and alkali-soluble novolak resin in this invention, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Monomethyl ether and diethylene glycol monoethyl ether. Propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate , Ethyl hydroxy acetate, 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate Ethyl pyruvate, ethyl acetate, butyl acetate and the like can be used. These organic solvents can be used individually or in combination of 2 or more types.

In addition, high boiling point solvents such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and benzyl ethyl ether It can be mixed and used.

Surfactant can be mix | blended with the positive photoresist composition of this invention in order to further improve applicability | paintability, such as striation.

As surfactant, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxy Polyoxyethylene alkyl allyl ethers such as ethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorb Sorbitan fatty acid esters such as non-trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Trioleate, polyoxyethylene sorbitan tristeare Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid esters, such as a salt, F-top EF301, EF303, EF352 (manufactured by Shinjuku Kogyo Co., Ltd.), Megapack F171, F173 (manufactured by Nippon Ink, Inc.), Florad FC430 , 431 (manufactured by Sumitomo Slime Co., Ltd.), fluorine-based surfactants such as Asahigard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Choza Co., Ltd.), and organosiloxane polymer KP341 ( Shinwol Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymerization polyflour №75, №95 (manufactured by Kogyo Holding Chemicals Co., Ltd.), and the like.

Among these surfactants, fluorine-based surfactants and silicone-based surfactants are particularly preferable. The compounding quantity of these surfactant is generally 2 weight part or less, preferably 1 weight part or less per 100 weight part of alkali-soluble resin and quinonediazide compound in the composition of this invention.

These surfactants may be added alone or in combination of several.

Examples of the developer of the positive photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, first amines such as ethylamine and n-propylamine, diethylamine, Second amines such as di-n-butylamine, third amines such as triethylamine and methyldiethylamine, and alcohol amines such as dimethylethanolamine and triethanolamine. Aqueous solutions of alkalis, such as quaternary ammonium salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, cyclic amines, such as a pyrrole and piperidine, can be used. Moreover, alcohols, such as isopropyl alcohol, and nonionic surfactant can also be added and used for the said aqueous solution of alkalis.

Among these developers, quaternary ammonium salts are more preferred, tetramethylammonium hydroxide and choline.

A light absorber, a crosslinking agent, an adhesion aid, etc. can be mix | blended with the composition for positive photoresists of this invention as needed. A light absorber is added as needed in order to prevent halation from a board | substrate, or to raise the visibility when it apply | coats to a transparent board | substrate. For example, a commercially available light absorber described in "Technology and Market of Industrial Dyes" (CMC Publishing) and Dye Section (Organic Synthetic Chemistry Association), for example, C.I. Disperse 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, CI Disperse 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, 73, 88, 117, 137, 143, 199 and 210, C.I. Disperse Violet 43, C.I. Disperse Blue 96, C.I. Fluorescent Brghtening Agents 112, 135 and 163, C. I Solvent Yellow 14, 16, 33 and 56, C. I Solvent Orange 2 and 45, C. I Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, C.I. Pigment Green 10, C.I. Pigment Brown 2 etc. can be used suitably. A light absorber is normally mix | blended in the ratio of 100 weight part or less, Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less with respect to 100 weight part of alkali-soluble resin.

The crosslinking agent is added in a range without affecting the formation of the positive image. The purpose of the crosslinking agent addition is mainly to adjust sensitivity, improve heat resistance, and improve dry etching resistance. Examples of the crosslinking agent include a compound in which formaldehyde is reacted with melamine, benzoguanamine, glycoluril, or the like, or an alkyl modified product thereof, an epoxy compound, an aldehyde, an azide compound, an organic peroxide, hexamethylenetetramine, or the like. These crosslinking agents may be blended in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight with respect to 100 parts by weight of the photosensitizer. When the compounding quantity of a crosslinking agent exceeds 10 weight part, since a sensitivity will fall and scum (resist residue) arises, it is unpreferable.

An adhesion aid is mainly added in order to improve the adhesiveness of a board | substrate and a resist, and especially to prevent a resist from peeling in an etching process. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylbinochlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinyl ethoxysilane, Alkoxysilanes such as difetyldimethoxysilane and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, Silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzoimidazole, indazole, already Heterocyclic compounds such as dozol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, 1, 1- Urea such as dimethylurea, 1,3-dimethylurea, or thiourea compounds.

These adhesive aids are mix | blended in the ratio of less than 10 weight part normally, Preferably it is less than 5 weight part with respect to 100 weight part of alkali-soluble resin.

The positive photoresist composition is applied to a substrate (e.g., a transparent substrate such as silicon / silicon dioxide coating, a glass substrate, an ITO substrate, etc.) by a suitable coating method such as a spinner or a coater so as to be used in the manufacture of the precision integrated circuit device. After prebaking, exposure through a predetermined mask, and post-processing (PEB: Post Bake) as necessary, a good resist can be obtained by developing, rinsing and drying.

Hereinafter, although the Example of this invention is shown, this invention is not limited to these. In addition,% represents weight% unless otherwise specified.

(Example)

Synthesis Example 1 Synthesis of Photosensitive Agent a

46.9 g of the following compound [I-19] and 53.7 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride were dissolved in 1 L of acetone and homogenized, followed by 21.2 g of triethylamine over 1 hour. It dripped. After completion of dropping, the mixture was stirred for 3 hours as it was. The obtained reaction mixture was crystallized in 4 L of 1% aqueous hydrochloric acid, and the precipitated yellow powder was collected by filtration. These were washed with water again and 87.9 g of the photosensitizer a which is the quinonediazide sulfonic acid ester of the compound [I-19] which is a target object was obtained.

Moreover, the area ratio of the diester of the photosensitive agent a was 60% in the high performance liquid chromatography measured using the detector using the ultraviolet-ray of 254 nm. The measurement of the said high-performance liquid chromatography happy carrier uses the LC-6A chromatography apparatus by Shimadzu Seisakusho Co., Ltd., Nova-PakCl8 (4 micrometers) 8 mm x 100 mm column by Waters, Inc. As a solvent, a solution of 68% acetonitrile, 30% distilled water, 1% triethylamine, and 1% phosphoric acid was flowed at a flow rate of 2 ml / min (hereinafter the same).

Synthesis Example (2): Synthesis of Photosensitive Agent b

65.7 g of the following compound [I-53] and 53.7 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride were dissolved in 1 L of acetone and homogenized, followed by 21.2 g of triethylamine over 1 hour. It dripped. After completion of dropping, the mixture was stirred for 3 hours as it was. The obtained reaction mixture was crystallized in 4 L of 1% aqueous hydrochloric acid solution, and the precipitated yellow powder was collected by filtration. These were washed with water further and 105.5 g of the photosensitizer b which is the quinone diazide sulfonic-acid ester of the compound [I-53] which is a target object was obtained.

Moreover, the area ratio of the diester of the photosensitive agent b was 52% in the high performance liquid chromatography measured using the detector using the ultraviolet-ray of 254 nm.

Synthesis Example (3): Synthesis of Photosensitive Agent c

111.5 g of the following compound [II-9] and 283.7 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride were dissolved in 2.5 L of acetone and homogenized, followed by splitting 6.5 g of 4-dimethylaminopyridine. Addition and 107.3 g of triethylamines were dripped over 1 hour. After completion of dropping, the mixture was stirred for 3 hours as it was. After stirring for 3 hours, distilled water is added to dissolve and homogenize the resulting salt, followed by stirring for 1 hour. The obtained reaction mixture was crystallized in 10 L of 1% aqueous hydrochloric acid solution, and the precipitated yellow powder was filtered. These were washed with water further and 350.2 g of the photosensitive agent c which is the quinonediazide sulfonic acid ester (complete ester body) of the compound [II-9] which is a target object was obtained.

Synthesis Example 4 Synthesis of Photosensitive Agent d

121.1 g of the following compound [II-1] and 283.7 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride were dissolved in 2.5 L of acetone and homogenized, and 6.5 g of 4-dimethylaminopyridine was separated. Addition and 107.3 g of triethylamines were dripped over 1 hour. After completion of dropping, the mixture was stirred for 3 hours as it was. After stirring for 3 hours, distilled water is added to dissolve the by-product salt to make it uniform, followed by stirring for 1 hour. The obtained reaction mixture was crystallized in 10 L of 1% aqueous hydrochloric acid, and the precipitated yellow powder was collected by filtration. The resultant was further washed with water to obtain 355.2 g of a photosensitive agent d which is a quinone diazide sulfonic acid ester (complete ester) of compound [II-1] as a target product.

Synthesis Example 5 Synthesis of Photosensitive Agent e

19 g of Yasuhara Chemical-made terpene-bis (2,6 xylenol) and 30 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride were dissolved in 800 ml of acetone and homogenized, followed by 4-dimethyl 1 g of aminopyridine was dropped and added dropwise over 11.1 g of triethylamine. After completion of dropping, the mixture was stirred for 3 hours as it was. After stirring for 3 hours, distilled water was added to dissolve the by-product salt to make it uniform, followed by stirring for 1 hour. The obtained reaction mixture was crystallized in 3 L of 1% aqueous hydrochloric acid, and the precipitated yellow powder was collected by filtration. These were washed with water further and 36 g of photosensitive agents e (complete ester body) which are target objects were obtained. In addition, the photosensitive agent e is a mixture containing [III-1-7], [III-2-3], and [III-3-3].

Synthesis Example 6 Synthesis of Photosensitive Agent f

After dissolving 16 g of teraben-bisphenol made by Yasuhara Chemical and 30 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride in 800 ml of acetone, after homogenizing, 1 g of 4-dimethylaminopyridine was added by decomposition, 11.1 g of triethylamine was dripped over 1 hour. After completion of dropping, the mixture was stirred for 3 hours as it was. After stirring for 3 hours, distilled water is added to dissolve the by-product salt to make it uniform, followed by stirring for 1 hour. The obtained reaction mixture was crystallized in 3 L of 1% aqueous hydrochloric acid, and the precipitated yellow powder was collected by filtration. These were washed with water further and 31 g of photosensitive agents f (complete ester body) which are target objects were obtained. In addition, the photosensitive agent f is a mixture containing [III-1-4], [III-2-1], and [III-3-1].

Synthesis Example (7): Synthesis of Comparative Photosensitive Agent g

According to the method of the synthesis example 11 of Unexamined-Japanese-Patent No. 2-103543, the quinonediazide complete ester body of the following polyhydroxy compound which is a comparative photosensitive agent g was synthesize | combined.

Synthesis Example 8 Synthesis of Comparative Photosensitive Agent h

According to the synthesis example 1 of Unexamined-Japanese-Patent No. 8-99952, the quinonediazide complete ester body of the following polyhydroxy compound which is a comparative photosensitive agent h was synthesize | combined.

Synthesis Example 9 Synthesis of Novolak Resin A

50 g of m-cresol,

50 g of p-cresol,

50 g of 37% formalin aqueous solution, and

Oxalic Acid 0.13g

The flask was put into a three neck flask, heated to 100 ° C while stirring, and reacted for 15 hours. Thereafter, the temperature was raised to 220 ° C., and the pressure was gradually reduced to 5 mm Hg to remove water, unreacted monomer, formaldehyde, oxalic acid, and the like. The molten alkali-soluble novolak resin was then returned to room temperature and recovered. Obtained novolak resin [A] was weight average molecular weight 7800 (polystyrene conversion), and dispersion degree was 5.6.

Synthesis Example (10): Synthesis of Novolak Resin B

50 g of m-cresol,

25 g of p-cresol,

28 g of 2,5-dimethylphenol

53 g of 37% formalin aqueous solution, and

Oxalic Acid 0.15g

The mixture was put into a three neck flask, heated to 100 ° C while stirring, and reacted for 14 hours.

Then, the temperature was raised to 200 ° C., and gradually reduced to 1 mmHg to remove water, unreacted monomer, formaldehyde, oxalic acid, and the like. The molten novolak resin was then returned to room temperature and recovered. The obtained novolak resin was weight average molecular weight 4800 (polystyrene conversion). Subsequently, 20 g of novolak resin was completely dissolved in 60 g of methanol, and then 30 g of water was slowly added thereto while stirring to precipitate the resin component. The upper layer was removed by decantation, the precipitated resin was collected, heated at 40 ° C, and dried under reduced pressure for 26 hours to obtain an alkali-soluble novolak resin [B]. The obtained novolak resin was weight average molecular weight 9680 (polystyrene conversion), and dispersion degree was 3.50.

Synthesis Example (11): Synthesis of Novolac Resin C

259.5 g of m-cresol,

9.7 g of p-cresol,

2,3-dimethylphenol 62.3 g

37% formalin aqueous solution 218.1 g

The flask was placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and stirred at 90 ° C to add 1.13 g of oxalic acid dihydrate. After 30 minutes, the bath temperature was raised to 130 ° C. and stirred for another 3 hours and 30 minutes to reflux the contents. Subsequently, the reflux condenser was replaced with a Liebig condenser, and the bath temperature was raised to 220 ° C. over about 1 hour to remove unreacted formalin, water, and the like. Furthermore, after performing atmospheric pressure removal for 1.5 hours, the pressure was gradually reduced to 1 mmHg to remove unreacted monomo and the like. It takes 2 hours to remove the reduced pressure.

The molten novolak resin was then returned to room temperature and recovered. The obtained novolak resin was weight average molecular weight 2360 (polystyrene conversion). Subsequently, 100 g of this novolak resin was completely dissolved in 1000 g of acetone, and then, 1000 g of n-hexane was added thereto under stirring, followed by further stirring for 30 minutes at room temperature, followed by standing for 1 hour. The lower layer was removed using a rotary evaporator to obtain a novolak resin (C). The obtained novolak resin was weight average molecular weight 5730 (polystyrene conversion), and dispersion degree was 2.6.

Synthesis Example 12 Synthesis of Novolak Resin D

11 g of p-cresol,

8 g of o-cresol,

69 g of 2,3-dimethylphenol,

20 g of 2,3,5-trimethylphenol,

2,6-dimethylphenol 4.9 g

Was mixed with 50 g of diethylene glycol monomethyl ether and placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. Subsequently, 85 g of 37% formalin aqueous solution was added and stirred while heating at a flow rate of 110 ° C. When the internal temperature reached 90 ° C., 6.3 g of oxalic acid dihydrate was added. Thereafter, the reaction was continued by maintaining the temperature of the flow rate at 130 ° C. for 18 hours, followed by removing the reflux condenser, distilling under reduced pressure at 200 ° C., and removing the unreacted monomer. Obtained novolak resin was M350 of 3350 and dispersion degree 2.55.

Preparation and Evaluation of Positive Photoresist Composition

[Examples 1-13, Comparative Examples 1-9]

In the photosensitizers a to f of the present invention obtained in the synthesis examples (1) to (6), the photosensitizers g and h of the comparative examples obtained in the synthesis examples (7) and (8), and the synthesis examples (9) to (12). The obtained novolak resin, solvent (ethyl sulfate / ethylethoxypropionate = 8/2), and a polyhydroxy compound (X or Z below) are shown in Tables 1 (Example) and 2 (Comparative Example). After mixing at the ratio and making it into a uniform solution, it filtered using the microfilter of 0.1 micrometer of pore diameters, and prepared the photoresist composition. This photoresist composition was apply | coated to various board | substrates based on the evaluation method of each following characteristic using the spinner.

TABLE 1

Polyhydroxy compound,

TABLE 2

(Evaluation method of swing width)

The unevenness | corrugation on an actual apparatus board | substrate was assumed, and the performance on an actual apparatus was estimated by the following model experiment.

41 resist-coated films (pre-baked: 90 ° C. hot plate 60 seconds) on a Bare Si substrate at intervals of 0.01 μm up to 0.800 to 1.200 μm, and 0.70 μm pitch at 0.98 μm (the peak of the exposure swing curve). The line width (CD) obtained when exposing film thicknesses other than them by the exposure energy and the same energy which reproduces the periodic pattern (mask) of the line and space (0.35 & 0.35 micrometer) of 1 to 1 ^* ). Then, the obtained value was graphed (film thickness at the time of film formation on the horizontal axis, and the CD calculated | required corresponding to each thickness of the horizontal axis on the vertical axis | shaft). From this graph, the swing width was defined as the CD change width for the film thickness change. And the switch width value of the comparative example 6 was normalized to 1, and the other swing width was shown by the relative evaluation with it. The smaller the value, the better the performance was not affected by the irregularities on the actual device substrate.

^*) (Profession from resist film formation to CD SEM measurement)

Prebaking (90 ° C hot plate 60 seconds) → Film thickness measurement → Exposure (NikonNSR-i9C (NA = 0.57, σ = 0.60) → Post-heating (PBE) 110 ° C / 60 seconds (hot plate) → 60 at 2.38% TMAH Paddle phenomenon in seconds → Rinse in pure water for 30 seconds → Spin dry → CD (scanning electron microscope (SEM) measurement)).

(Evaluation method of phenomenon defect)

Each resist film was applied at 0.98 mu m on a 6-inch Bare Si substrate, and dried at 90 DEG C for 60 seconds on a vacuum adsorptive plate. Next, it exposed with the Nikon NSR-i9C stepper through the test mask of a 0.40 micrometer contact hole pattern (Hole Duty ratio = 1: 3). Subsequently, after 60 seconds of paddle development in 2.38% TMAH (tetramethylammonium hydroxide aqueous solution), the mixture was washed with pure water for 30 seconds and spin-dried. The development defect function of the sample obtained in this way was measured with KLA-2112 by KLC Corporation, and the obtained primary data value is made into the development defect function.

(Evaluation method of side lobe light resistance by halftone mask exposure)

Each resist film was applied at 0.98 mu m on a 4 inch Bare Si substrate, and dried at 90 DEG C for 60 seconds on a vacuum suction hot plate. Next, it exposed with the Nikon NSR-i9C stepper through the halftone mask (80% of transmittance) of 0.40 micrometer contact hole (Hole Duty ratio = 1: 3). Subsequently, after 60 seconds of paddle development at 2.38% TMAH, water was washed for 30 seconds in pure water to obtain an image by spin drying. By defining this time, the minimum amount of exposure which is the size of the transfer 0.40㎛ contact holes (mask) the optimum exposure amount E _opt in, and back side lobe light to reproduce on the substrate the resist on the resist substrate with a _limit E, their ratio E _limit / E _opt was used as an index of side lobe light resistance. At this time, the value of the comparative example 6 was normalized to 1, and the other side lobe light tolerance was shown by the relative evaluation.

Larger values indicate better sidelobe light resistance, and smaller values are weaker.

(Evaluation method of remaining standing wave)

Visual determination by SEM photograph of the cross section of the resist pattern (0.98 micrometer film thickness) on the swing obtained by the swing width evaluation method.

(Circle): Good, (triangle | delta): It was observed, but it appeared a little, ×: It was remarkably observed, × x: There exists a problem more than x.

Each characteristic mentioned above was evaluated. The results are shown in Table 3.

TABLE 3

As a result of Table 3, the Example of this invention showed the outstanding performance in each evaluation. And the comparative example did not satisfy the whole performance, and especially the side lobe light tolerance by halftone mask exposure was inadequate.

By the positive photoresist composition of the present invention, the oscillation width (swing width) of the line width with respect to the variation of the film thickness is narrow, and has high resolution, and also the halftone phase difference shift mask aptitude (side lobe resistance) which was not compatible in the past is good. Excellent resist performance with less development defects and less residual standing waves is obtained.

Claims (5)

In a positive photoresist composition containing an alkali-soluble resin, a quinonediazide sulfonic acid ester photosensitive agent and an alkali-soluble low molecular compound, the quinonediazide sulfonic acid ester photosensitive agent is (A) The diester body of the quinone diazide of the phenolic low molecular weight compound which has 3-6 phenolic hydroxyl groups represented by following General formula [I]; And (B) contains the complete ester of quinone diazide represented by the following general formula [II] or [III-1]-[III-3], In high-performance liquid chromatography measured using a detector using ultraviolet light at 254 nm, the area ratio of the pattern area of the diester body of the above (A) to the total pattern area of the photosensitive agent is 25% or more and less than 50%, The area ratio of the complete ester of said (B) is 3% or more and 60% or less, The positive photoresist composition characterized by the above-mentioned. General formula [1] (R ₁ ~R _4: may be the same and different and each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, A may be the same and different and are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, or when m is 2 or more, a plurality of R ₅ or R _6: R _5, R ₆ Each may be same or different, R ₇ : represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, and when m is 2 or more, each of the plurality of R ₇ may be the same or different; A: It may be the same or different and is a single bond, -O-, -S-, -SO-, -SO _2- , -CO-, -CO _2- , -C (R ₈ ) (R ₉ )- , -N (R ₁₀ )-, -N (R ₁₀ ) SO ₂ -represents a single group or a combination of two or more thereof, R ₈ and R _{9 may be the} same or different, may represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ₈ and R ₉ may be bonded to each other to form a cycloalkyl group, R ₁₀ : represents a hydrogen atom, an alkyl group, m: integer of 1-4) General formula [II] (R ₁₁ to R ₁₂ : same or above, -OQ (Q represents a naphthoquinone diazide-5- (and / or -4-) sulfonyl group below), R ₁₃ to R _{17 may be the} same or different and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, an acyloxy group, a halogen, a nitro group, or a cyano group , A cyclohexyl group or -OQ (Q is the same as above), R ₁₈ to R _{21 may be the} same or different and represent an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyloxy group, or a cyclohexyl group. However, in General Formula [II], the number of Q is two or more and less than six.) (Q: same as above, R _{22 may be the} same or different and represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group or an acyloxy group, R <_{23> may be} same or different, and represents a hydrogen atom and an alkyl group, x: represents the integer of 1-3, y: represents the integer of 1-6.) The positive photoresist composition according to claim 1, wherein an area ratio of the diester pattern area to the total pattern area is 25% or more and less than 40%. The positive photoresist composition according to claim 1, wherein an area ratio of the diester pattern area of the above (A) to the total pattern area is 28% or more and 38% or less. The positive photoresist composition according to claim 1, wherein an area ratio of the entire ester area of the (B) to the total pattern area is 4% or more and 50% or less. The positive photoresist composition according to claim 1, wherein an area ratio of the entire ester area of the (B) to the total pattern area is 5% or more and 40% or less.