JPH06289614A - Negative radiation sensitive resist composition - Google Patents

Abstract

PURPOSE:To attain excellent resolution, profile shape, sensitivity and to suppress influence due to the reflected light from a substrate. CONSTITUTION:This resist composition is made by containing an alkali soluble resin (A), an alkoxymethylated amino resin (B), a triazine compound (C) expressed by a formula I (each of R<1>, R<2> and R<3> is hydrogen atom or lower alkyl group, (n) is 0 or 1) and, if necessary, a benzophenone based compound (D) expressed by a formula II (each of R<4> and R<5> is hydrogen atom or lower alkyl group, (m) is 1-3).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel negative-working radiation-sensitive resist composition. More specifically, the present invention has high resolution and is excellent in the profile shape of the resist pattern, and also has a negative sensitivity radiation sensitive resist composition having high sensitivity, and further has the above-mentioned characteristics,
The present invention relates to a negative radiation-sensitive resist composition capable of suppressing the effects of reflected light from a substrate (effects of standing waves, notching phenomenon).

[0002]

2. Description of the Related Art In recent years, the progress of high density and high integration of semiconductor devices has been remarkably advanced, and the resolution in the fine processing technology has been required up to the submicron region. Also, with respect to the lithography technique which is the mainstream in the field of manufacturing semiconductor devices, fine processing of 0.5 μm or less is required, and in order to meet this, Deep UV, i.
Light sources emitting 200 to 500 nm wavelength such as X-rays and g-rays and excimer lasers such as KrF laser (wavelength 248 nm) have begun to be used, and development of resists sensitive to electron beams and X-rays is underway.

Further, a negative resist composition which is compatible with such radiation has been actively researched. For example, it is composed of a phenol novolac resin and a bisazide compound which are sensitive to Deep UV, i rays and g rays. A composition, a composition comprising a mixture of chloromethylated polystyrene or polyvinylphenol and an aromatic bisazide compound, which is sensitive to excimer laser (Japanese Patent Publication No. 62-8777), excimer laser,
Deep UV, a resist composition comprising a thermosetting resin that is sensitive to X-rays and a halogenated organic compound that absorbs actinic radiation in the wavelength range of 210 to 299 nm as a photoacid generator (JP-A-62-16405). ), And as a resist composition sensitive to electron beams, polymethyl methacrylate (Japanese Patent Publication No. 45-30225), polyglycidyl methacrylate [[Journal.
Of Electrochemical Society (JEC)
S) "Vol. 118, p. 669 (1971)],
Chloromethylated polystyrene (JP-A-57-17603)
No. 4) has been proposed as a component.

However, in these resist compositions, the cross-sectional shape of the resist pattern obtained from the resist composition is apt to have a rounded profile and the top tends to have a rounded profile shape, and high resolution cannot be obtained.
There is also a drawback that it has no practical sensitivity to radiation such as UV, i-ray, g-ray, excimer laser, electron beam and X-ray. Therefore, in the field of manufacturing semiconductor devices, there has been a strong demand for the development of a negative radiation-sensitive resist composition having excellent resolution and resist pattern profile shape and high sensitivity to various radiations.

Therefore, the inventors of the present invention have responded to such a demand and are sensitive to various radiations, have a high resolution, are excellent in the profile shape of a resist pattern, and have a high sensitivity. Was previously proposed (JP-A-4-136858, JP-A-4-1368).
59, JP-A-4-136860).

However, these compositions have not been sufficiently satisfactory in terms of resolution, profile shape of resist pattern, sensitivity, and suppression of influence of light reflected from the substrate.

[0007]

Under the circumstances, the present invention provides a negative-working radiation-sensitive resist composition having high resolution, excellent resist pattern profile shape, and high sensitivity. In addition to having the above characteristics,
The present invention has been made for the purpose of providing a negative radiation-sensitive resist composition capable of suppressing the effects of reflected light from a substrate (the effects of standing waves, notching development).

[0008]

Means for Solving the Problems As a result of intensive studies to develop a negative radiation sensitive resist composition having the above-mentioned preferable properties, the present inventors have found that an alkali-soluble resin,
A composition containing an alkoxymethylated amino resin and a triazine compound having a specific structure has excellent high resolution and provides a resist pattern profile shape, and also has high sensitivity, and further specified in the composition. It was further found that the compound containing the benzophenone compound having the structure of 1) can suppress the influence of the reflected light from the substrate. The present invention has been completed based on such findings.

That is, the present invention comprises (A) an alkali-soluble resin, (B) an alkoxymethylated amino resin, and (C).
General formula

[Chemical 4] (Wherein R ¹ , R ² and R ³ are each a hydrogen atom or a lower alkyl group, which may be the same or different, and n is 0 or 1) and the case (D) General formula

[Chemical 5] (Wherein R ⁴ and R ⁵ are each a hydrogen atom or a lower alkyl group, and they may be the same or different, and m is an integer of 1 to 3). The present invention provides a negative radiation sensitive resist composition.

The alkali-soluble resin used as the component (A) in the composition of the present invention is not particularly limited, and examples thereof include novolac resins, acrylic resins, copolymers of styrene and acrylic acid, and polyhydroxystyrene resins. Among them, polyhydroxystyrene resin and novolac resin are preferable among them, and particularly when polyhydroxystyrene resin is used, the sensitivity of the resist is significantly improved and a resist pattern having an excellent profile shape is obtained. Therefore, it is advantageous.

As the novolak resin, those conventionally used as film-forming substances in conventional positive photoresist compositions, for example, aromatic hydroxy compounds such as phenol, cresol and xylenol, and formaldehyde, acetaldehyde, benzaldehyde, terephthalaldehyde, etc. Those obtained by condensing the aldehydes of 1 above in the presence of an acidic catalyst are used. This alkali-soluble novolak resin has a weight average molecular weight of 2,000 to 20,000, preferably 3,000 to 15 with the low molecular region cut.
Those in the range of 000 are preferable.

Such an alkali-soluble novolac resin is often used as a resin component of a resist composition. In the present invention, when the profile shape of the resist pattern is taken into consideration, 30% by weight of m-cresol is used.
Those obtained using a phenolic compound containing the above, especially containing 55 to 75% by weight of m-cresol, and the remaining components of p-cresol, 2,5-xylenol and 3,5-xylenol Those obtained from the mixed phenolic compound containing at least one selected from the group of 45 to 25% by weight are preferable.

On the other hand, examples of the polyhydroxystyrene resin include modified polyhydroxystyrene and hydrogenated polyhydroxystyrene, and hydrogenated polyhydroxystyrene is particularly preferable.

Examples of the modified polyhydroxystyrene include polyhydroxystyrene, for example, benzenesulfonyl chloride derivative, naphthalenesulfonyl chloride derivative,
Examples thereof include those obtained by reacting a benzene carbonyl chloride derivative and a naphthalene carbonyl chloride derivative in the presence of a basic catalyst. Specific examples of the sulfonyl chloride derivative and the carbonyl chloride derivative include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, and
Examples thereof include p-acetaminobenzenecarbonyl chloride, benzenecarbonyl chloride, p-chlorobenzenecarbonyl chloride and naphthylbenzenecarbonyl chloride. In this case, polyhydroxystyrene 100
With respect to parts by weight, the sulfonyl chloride derivative and the carbonyl chloride derivative are usually 10 to 30 parts by weight,
It is preferably used in a proportion of 15 to 25 parts by weight. Such modified polyhydroxystyrene has a weight average molecular weight of 3,000 to 50,000, preferably 5,000 to 300.
In the range of 00.

On the other hand, hydrogenated polyhydroxystyrene is
Usually a general formula,

[Chemical 6] (Wherein R is a halogen atom, a hydroxyl group, a nitro group, a lower alkyl group or a lower alkoxy group, k is 0 or an integer of 1 to 4), and a phenolic structural unit represented by the general formula

[Chemical 7] (R and k in the formula have the same meanings as described above) and a cyclic alcohol-based structural unit is mainly contained. It can be produced by hydrogenating styrene by a known method. The hydrogenation rate at this time is 1 to 40 mol%, preferably 15 to 30 mol%
It is desirable to be in the range of. If this hydrogenation rate is less than 1 mol%, the transparency at short wavelengths such as i-line, deep UV region and excimer laser is insufficient, and if it exceeds 40 mol%, the dry etching resistance decreases and alkali It is not preferable because the solubility in a developing solution decreases.

In the present invention, the above general formula (III)
In and (IV), hydrogenated poly (4-hydroxystyrene) with k = 0 is preferred. The weight average molecular weight (Mw) of the hydrogenated polyhydroxystyrene is usually 3
000 to 15,000, preferably 5,000 to 10,000
It is selected in the range of. If the weight average molecular weight is less than 3,000, mechanical properties and dry etching resistance are deteriorated, and if it exceeds 15,000, workability is deteriorated.

Further, as the hydrogenated polyhydroxystyrene, those purified by the following two methods are particularly preferable. The first method is to dissolve the hydrogenated polyhydroxystyrene in a polar solvent, add an aliphatic hydrocarbon solvent to the solution, shake the mixture sufficiently, and then separate the layers to collect only the polar solvent layer. The solvent is removed from this layer to obtain hydrogenated polyhydroxystyrene as a residue.

Examples of the polar solvent used in this case include ethyl lactate, N-methylpyrrolidone, dimethylimidazolidinone, dimethylacetamide, dimethylformamide and the like, which are phase-separated from the aliphatic hydrocarbon solvent. You may use 1 type and may use it in combination of 2 or more type. The amount of the polar solvent used is usually selected so that the concentration of hydrogenated polyhydroxystyrene is 1 to 50% by weight. Further, if necessary, the hydrogenated polyhydroxystyrene may be dissolved by heating.

As the aliphatic hydrocarbon solvent added to the solution thus obtained, for example, pentane, 2
-Methylbutane, n-hexane, 2-methylpentane,
2,2-dibutylbutane, 2,3-dibutylbutane, n
-Heptane, n-octane, isooctane, 2,2,3
-Trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, etc. may be used, and these may be used alone or in combination of two or more.

These aliphatic hydrocarbon solvents are usually added to the polar solution at a ratio of 100 to 500 parts by weight to 100 parts by weight of the polar solvent, shaken well, and then allowed to stand to separate into two layers. To do. By this operation, the polar solvent layer is usually separated into the lower layer and the aliphatic hydrocarbon solvent layer is separated into the upper layer, and in the upper aliphatic hydrocarbon solvent layer, cyclic alcohol which becomes a factor of the residue after resist development is formed. A low molecular weight region containing a large amount of system structural units is extracted and contained.

The polymer contained in the lower polar solvent layer is recovered and used for a resist by a known method, for example, a method of depositing the polymer in a poor solvent such as water or a method of distilling off the solvent. Used as a binder. When a resist solvent such as ethyl lactate is used as the polar solvent, the concentrated one can be used as it is.

On the other hand, the second method is a method utilizing the difference in solubility in a solvent between the portion containing a large amount of cyclic alcohol structural units and the portion not containing the same in the hydrogenated polyhydroxystyrene. Lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol are used.
These lower aliphatic alcohols may be used alone,
You may use it in combination of 2 or more type. The amount of the lower aliphatic alcohol used is usually selected in the range of 100 to 500 parts by weight with respect to 100 parts by weight of hydrogenated polyhydroxystyrene.

The hydrogenated polyhydroxystyrene is added to the lower aliphatic alcohol and dissolved, and then allowed to stand. At this time, if necessary, heating and dissolution may be carried out, followed by cooling and standing. By this operation, a portion containing a large amount of cyclic alcohol-based structural units is deposited, so after removing the deposits by a known means, the residual liquid is poured into a poor solvent such as water to deposit the polymer, and the resist is recovered. The binder may be used as the binder, or the resist solvent may be used as it is.

The resist composition using the purified hydrogenated polyhydroxystyrene thus obtained has a high transparency in the short wavelength region and can form a resist pattern having no residue.

In the composition of the present invention, the alkali-soluble resin as the component (A) may be used alone or in combination of two or more kinds.

In the composition of the present invention, an alkoxymethylated amino resin is used as the component (B). Particularly preferable examples of the alkoxymethylated amino resin include an alkoxymethylated melamine resin and an alkoxymethylated urea resin. These alkoxymethylated amino resins, for example, after reacting melamine or urea with formalin in a boiling aqueous solution to obtain a condensate,
It can be prepared by etherifying this with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and then cooling the reaction solution to take out the precipitated resin.

The type of the alkoxymethylated amino resin is not particularly limited, and examples thereof include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, Examples thereof include ethoxymethylated urea resin, propoxymethylated urea resin and butoxymethylated urea resin. These may be used alone or in combination of two or more.

Among the above-mentioned alkoxymethylated amino resins, a mixture of an alkoxymethylated melamine resin and an alkoxymethylated urea resin is particularly preferable, and the mixing ratio thereof is 1 part by weight of the alkoxymethylated melamine resin.
It is preferably 7 to 10 parts by weight of alkoxymethylated urea resin. This alkoxymethylated melamine resin is obtained by converting a methylol group of a methylolated melamine obtained by a conventional method into an alkoxymethyl group, and advantageously has an average of 2.5 or more methylol groups, preferably 3. It is a melamine resin that is converted to 5 or more alkoxymethyl groups. Practically commercially available Nikarac Mx-
750, Nikarac Mx-706, Nikarac Mx-1
01, Nicarax Mx-032, Nicalax Mx-70
8, Nicalaque Mx-40, Nicalaque Mx-31, Nicalaque Ms-11, Nicalaque Mw-22, Nicalaque Mw-30 (above, Sanwa Chemical Co., Ltd.), etc. can be preferably used. These may be used alone or in combination of two or more. As the alkoxymethylated urea resin, a commercial product such as Mx-290 (manufactured by Sanwa Chemical Co., Ltd.) can be used.

The weight ratio of the alkali-soluble resin (A) and the alkoxymethylated amino resin (B) is 60:40 to 95: 5, preferably 75:25.
It is desirable to use it in such a ratio that it becomes 90 to 90:10.

In the composition of the present invention, as the component (C), a compound represented by the general formula

[Chemical 8] The triazine compound represented by is used.

In the general formula (I), R ¹ , R ² and R ³ are each a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, and they may be the same or different. May be. Further, n is 0 or 1. This triazine compound has been conventionally used in JP-A-2-146044 and JP-A-2-217855.
Japanese Patent Laid-Open No. 4-136858 and Japanese Patent Laid-Open No. 4-1858
Compared with the triazine compound described in Japanese Patent No. 36859,
It has a structural and physical characteristic that it contains a piperonyl group, which can greatly improve the sensitivity of the resist composition.

The triazine compound may be any one as long as it has a structure represented by the general formula (I), but it is particularly preferable that R ¹ , R ² and R ³ are all hydrogen atoms. Is.

In the present invention, the triazine compound as the component (C) may be used alone or in combination of two or more, and the compounding amount thereof is the same as that of the component (A) ( It is usually selected in the range of 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the component B). If the blending amount is less than 0.5 part by weight, the crosslinking reaction does not proceed sufficiently and the desired pattern cannot be obtained.
If it exceeds 5 parts by weight, the solubility of the resist in an alkaline aqueous solution is deteriorated and the developability is lowered, which is not preferable.

In the composition of the present invention, in addition to the components (A), (B) and (C), if necessary,
As the component (D), a general formula

[Chemical 9] A benzophenone compound represented by can be added.

In the general formula (II), R ⁴ and R
Each of ⁵ is a hydrogen atom or a lower alkyl group such as a methyl group or an ethyl group, which may be the same or different. Further, m is an integer of 1 to 3.

The resist composition containing such a benzophenone-based compound has a high resolution especially when a highly reflective substrate such as a substrate having aluminum deposited on a silicon wafer or a substrate having gold deposited on a silicon wafer is used. The reflected light can be suppressed without deteriorating the resist pattern profile shape and the resist characteristics such as sensitivity, and as a result, the standing wave effect can be suppressed and the notching phenomenon can be suppressed.

Examples of the benzophenone compound represented by the general formula (II) include 4-amino-2'-hydroxybenzophenone, 4-amino-4'-hydroxybenzophenone, 4-amino-6'-hydroxybenzophenone, 4 -Dimethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-hydroxybenzophenone, 4-dimethylamino-6'-hydroxybenzophenone, 2-dimethylamino-2 ', 4'-
Dihydroxybenzophenone, 4-dimethylamino-
2 ', 4'-dihydroxybenzophenone, 6-dimethylamino-2', 4'-dihydroxybenzophenone,
2-diethylamino-2 ', 4'-dihydroxybenzophenone, 4-diethylamino-2', 4'-dihydroxybenzophenone, 6-diethylamino-2 ', 4'
-Dihydroxybenzophenone, 2-dimethylamino-
2 ', 4', 6'-trihydroxybenzophenone, 4
-Dimethylamino-2 ', 4', 6'-trihydroxybenzophenone, 6-dimethylamino-2 ', 4',
6'-trihydroxybenzophenone and the like can be mentioned. Particularly preferred among these is 4-dimethylamino-2 ', 4'-dihydroxybenzophenone.

In the composition of the present invention, the benzophenone compound as the component (D) may be used alone or in combination of two or more, and the compounding amount thereof is
The amount is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). If the blending amount is less than 0.1 part by weight, the effect of suppressing reflected light is sufficiently exhibited, and if it exceeds 10 parts by weight, the effect is not improved for the amount,
Rather, the storage stability tends to deteriorate.

The composition of the present invention contains, if necessary, compatible additives such as an additional resin, a plasticizer for improving the performance of the resist film, etc., within a range that does not impair the object of the present invention. Stabilizers, surfactants, coloring agents for making the developed image more visible, and conventional additives such as sensitizers and antihalation dyes for further enhancing the sensitizing effect be able to.

The composition of the present invention is advantageously used in the form of a solution by dissolving each of the above components in an organic solvent.

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexanone, isobutyl methyl ketone, isoamyl methyl ketone, 1,1,1.
Ketones such as 1-trimethylacetone; polymethyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate or diethylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether or monophenyl ether. Dihydric alcohols and derivatives thereof; cyclic ethers such as dioxane; and esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, ethyl 3-ethoxypropionate Can be mentioned. These may be used alone or in combination of two or more.

Next, a method of forming a fine pattern using the solution of the negative-working radiation-sensitive resist composition thus prepared will be described. First, the resist composition is formed on a substrate such as a silicon wafer. Solution is applied with a spinner or the like and dried to form a radiation sensitive layer, and then g-line, i-line, Deep UV, excimer laser,
After selectively irradiating an X-ray through a mask or scanning and irradiating with an electron beam, heat treatment is performed, and then,
For example, by developing an organic alkaline aqueous solution such as 2 to 10% by weight of tetramethylammonium hydroxide or choline using an alkaline aqueous solution, a portion not irradiated with radiation is selectively dissolved and removed, and a resist pattern having an excellent profile shape is formed. Can be formed.

[0043]

According to the present invention, by using the triazine compound represented by the general formula (I) in place of the conventional triazine compound, the resolution and profile shape characteristics are excellent, and the sensitivity is greatly increased. You can
Further, by further blending a benzophenone compound represented by the general formula (II), the resolution, profile shape, and sensitivity characteristics are excellent, and the reflected light of the highly reflective substrate can be suppressed, and the standing wave effect and notching phenomenon ( It is possible to suppress the deformation of several linear resist patterns formed in parallel on the substrate.

[0044]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

The physical properties of the negative type radiation sensitive resist composition were determined as follows. (1) Sensitivity: A sample was coated on a silicon wafer using a spinner and dried on a hot plate at 70 ° C. for 90 seconds to form a 1.50 μm thick resist layer. Next, i-line reduction projection exposure apparatus NSR1755
1 using i7B [NA = 0.54] (manufactured by Nikon Corporation)
After selectively exposing the i-line at intervals of 0 ms to 5 ms, a heat treatment was performed at 90 ° C. for 90 seconds. Next, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used for paddle development for 65 seconds, followed by washing for 30 seconds with water and drying to obtain a resist pattern. 0.6 in that case
The minimum exposure time required to obtain a pattern size of μm was defined as the sensitivity.

(2) Resolution: The minimum resist pattern size that is resolved when exposed with the exposure amount set to the above sensitivity.

(3) Profile shape: A sample was coated on a silicon wafer using a spinner and dried on a hot plate at 70 ° C. for 90 seconds to give 1.50.
A resist layer having a thickness of μm was formed. Next, i-line reduction projection exposure apparatus NSR1755i7B [NA = 0.54]
(Manufactured by Nikon Corporation), the i-line is selectively exposed at intervals of 10 ms to 5 ms, and then 90 ° C. at 90 ° C.
Heat treatment was performed for a second. Next, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used for paddle development for 65 seconds, followed by washing for 30 seconds with water and drying to obtain a resist pattern. By observing a SEM (scanning electron microscope) photograph in which a resist pattern of 0.6 μm line and space was obtained, ⊚ indicates that the resist pattern is rectangular, and ∘ indicates that the resist pattern is almost rectangular. Those having an inverse taper shape were marked with x.

(4) Standing wave effect: By observing a SEM (scanning electron microscope) photograph of a resist pattern of 0.6 μm line and space obtained under the same conditions as in (3) above, the side surface of the resist pattern was observed. The case where there was no wavy unevenness and the effect of standing waves was suppressed was marked with ◯, and the case where wavy unevenness appeared on the side surface of the resist pattern and the effect of standing waves appeared was marked with x.

(5) Notching phenomenon: SEM of several linear resist patterns formed in parallel on the plane of the sample
When observed with a (scanning electron microscope), no deformation was observed, and ◯ was given when each straight line was distorted.

Reference Example 1 Maruka Linker P which is hydrogenated polyhydroxystyrene
HM-C [hydrogenation rate 20 mol%, weight average molecular weight 800
0] (manufactured by Maruzen Petrochemical Co., Ltd.) to 150 g of ethyl lactate
Dissolve this in a separatory funnel, then add 150 g of n-hexane, shake well, and let stand to allow n-hexane layer (upper layer) and ethyl lactate layer (lower layer).
And separated. Then, the upper n-hexane layer was removed, 150 g of n-hexane was added to the remaining ethyl lactate layer, the same operation was repeated 3 times, and the obtained ethyl lactate layer was added dropwise to 2 liters of pure water. The precipitated product was collected, washed with pure water, and dried to obtain purified hydrogenated polyhydroxystyrene.

Reference Example 2 Maruka Linker P which is hydrogenated polyhydroxystyrene
HM-C [hydrogenation rate 20 mol%, weight average molecular weight 800
0] (Maruzen Petrochemical Co., Ltd.) 50 g of methyl alcohol 2
The precipitate was dissolved in 100 g, shaken well, and then the filtrate obtained by filtration was added dropwise to 2 liters of pure water to collect the precipitated product, which was washed with pure water, dried and purified. Hydrogenated polyhydroxystyrene was obtained.

Reference Example 3 m-cresol and p-cresol in a weight ratio of 70: 3
The mixture was mixed at a ratio of 0, formalin was added to the mixture, and the cresol novolac resin obtained by condensation by an ordinary method using an oxalic acid catalyst was subjected to a fractionation treatment to cut the low molecular weight region to obtain a weight average molecular weight of 6000. A cresol novolac resin was obtained.

Reference Example 4 As poly (4-hydroxystyrene), 100 g of linker M (manufactured by Maruzen Petrochemical Co., Ltd.) and 20 g of p-acetaminobenzenesulfonyl chloride were added to dimethylacetamide 5
A solution obtained by dissolving 12.66 g of triethylamine in 40 g of dimethylacetamide was added dropwise over 30 minutes while being dissolved in 00 g and then stirred at room temperature. afterwards,
Further, the mixture was reacted at room temperature for 5 hours while stirring. Next, the formed salt that has precipitated in the reaction solution is removed by filtration, the filtrate is added dropwise to 5 liters of cold water to collect the precipitated product, which is washed with water and dried to obtain the target modified polyhydroxy compound. Styrene was obtained.

Example 1 8.0 g of purified hydrogenated polyhydroxystyrene obtained in Reference Example 1 and Mx-29 which is a methoxymethylated urea resin
0 (manufactured by Sanwa Chemical Co., Ltd.) 1.80 g and Mx-750 which is a methoxymethylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
After 0.20 g was dissolved in 32 g of ethyl lactate, 2.5 g of the following triazine compound was dissolved to obtain a resist solution.

[0055]

[Chemical 10]

Next, this resist solution was left in an atmosphere of hexamethyldisilazane for 7 minutes and spin-coated on a 6-inch silicon wafer surface-treated for 20 seconds at 4000 rpm, and the sensitivity, resolution and profile shape were determined by the above-mentioned method. The physical properties of The results are shown in Table 1.

Examples 2 to 4 A resist was prepared in the same manner as in Example 1 except that the purified hydrogenated polyhydroxystyrene in Example 1 was replaced with the resin obtained in Reference Example 2, Reference Example 3 or Reference Example 4. A solution was obtained. Then, the resolution, sensitivity, and physical properties of the profile shape of the resist pattern were obtained by the same method as in Example 1. The results are shown in Table 1.

Example 5 A resist solution was obtained in the same manner as in Example 1 except that the triazine compound was changed to the following triazine compound. Then, the resolution, sensitivity, and physical properties of the profile shape of the resist pattern were obtained by the same method as in Example 1. The results are shown in Table 1.

[0059]

[Chemical 11]

Examples 6 to 8 Resists were obtained in the same manner as in Example 5 except that the purified hydrogenated polyhydroxystyrene in Example 5 was replaced by the resin obtained in Reference Example 2, Reference Example 3 or Reference Example 4. A solution was obtained. Then, in the same manner as in Example 5, the resolution, sensitivity and profile physical properties of the resist pattern were obtained. The results are shown in Table 1.

Comparative Example 1 In Example 1, the triazine compound was added to 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl)-
A resist solution was obtained in the same manner as in Example 1 except that 1,3,5-triazine was used. Then, the resolution, sensitivity, and physical properties of the profile shape of the resist pattern were obtained by the same method as in Example 1. The results are shown in Table 1.

[0062]

[Table 1]

Example 9 8.0 g of the purified hydrogenated polyhydroxystyrene obtained in Reference Example 1 and Mx-29 which is a methoxymethylated urea resin
0 (manufactured by Sanwa Chemical Co., Ltd.) 1.80 g and Mx-750 which is a methoxymethylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
0.20 g and 4-dimethylamino-2 ', 4'-dihydroxybenzophenone 2 g were dissolved in ethyl lactate 32 g, and then the following triazine compound 2.5 g was dissolved to obtain a resist solution.

[0064]

[Chemical 12]

Next, this resist solution was vapor-deposited with gold 6
Inch silicon wafer was spin coated at 4000 rpm for 20 seconds, and the sensitivity, resolution, and
The physical properties of profile shape, standing wave effect and notching phenomenon were sought. The results are shown in Table 2.

Examples 10 to 12 Resists were obtained in the same manner as in Example 9 except that 4-dimethylamino-2 ', 4'-dihydroxybenzophenone in Example 9 was replaced with another compound represented by the general formula (II). A solution was obtained. Then, in the same manner as in Example 9, the resist pattern resolution, sensitivity, profile shape, standing wave effect, and physical properties of notching phenomenon were determined. The results are shown in Table 2.

Comparative Example 2 In Example 9, 4-dimethylamino-2 ', 4'-
A resist solution was obtained in the same manner as in Example 9 except that dihydroxybenzophenone was changed to the following compound. Then, in the same manner as in Example 9, the resist pattern resolution, sensitivity, profile shape, standing wave effect, and physical properties of notching phenomenon were determined. The results are shown in Table 2.

[0068]

[Chemical 13]

[0069]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etsuko Iguchi 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd.

Claims (5)

[Claims] 1. (A) an alkali-soluble resin, (B) an alkoxymethylated amino resin, and (C) a general formula: (Wherein R ¹ , R ² and R ³ are each a hydrogen atom or a lower alkyl group, which may be the same or different and n is 0 or 1). A negative radiation-sensitive resist composition comprising 2. (A) an alkali-soluble resin, (B) an alkoxymethylated amino resin, (C) a general formula: (Wherein R ¹ , R ² and R ³ are each a hydrogen atom or a lower alkyl group, which may be the same or different, and n is 0 or 1), and (D) General formula: (Wherein R ⁴ and R ⁵ are each a hydrogen atom or a lower alkyl group, and they may be the same or different, and m is an integer of 1 to 3). A negative radiation-sensitive resist composition comprising 3. The negative radiation-sensitive resist composition according to claim 1, wherein the alkali-soluble resin is at least one selected from novolac resins and polyhydroxystyrene resins. 4. The negative radiation-sensitive resist composition according to claim 3, wherein the alkali-soluble resin is a polyhydroxystyrene resin. 5. The negative radiation-sensitive resist composition according to claim 4, wherein the polyhydroxystyrene resin is hydrogenated polyhydroxystyrene.