JPH07179754A - Composition for forming electrically conductive agent and method for forming pattern - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of preventing deactivation of an acid of a chemical amplification type resist, checking electrification during exposure to charged radiation, comprising a sulfonated polyaniline, a solvent, an amine, a sulfone group-containing component in a specific ratio, respectively. CONSTITUTION:This compound comprises (A) 0.1-20 pts.wt. of a sulfonated polyanlline having 20-80% sulfone group content based on the aromatic ring (preferably one having 500-100,000 molecular weight), (B) 100 pts.wt. of a solvent, (C) 0.01-10 pts.wt. of an amine [e.g. a compound of formula I (R1 to R4 each is H, a 1-4C alkyl, CH2OH, NH2, etc.), etc.] and/or a quaternary ammonium salt [e.g. a compound of formula II (R1 to R4 each is H or a 1-4C alkyl; X is OH, 1/2SO<2->4, NO3, etc.) and (D) 0.001-100 pts.wt. of a sulfone group-containing compound and/or polymer (preferably an ammonium salt).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive agent forming composition and a pattern forming method using the same.

[0002]

2. Description of the Related Art Recently, a chemically amplified resist has been attracting attention and studied as a resist material for manufacturing a semiconductor device. This type of resist contains as a component a substance that generates an acid upon irradiation with ionizing radiation, and is characterized in that the reaction in the resist is catalytically promoted by this acid. For this reason, the sensitivity is high, and the resolution has improved due to the results of many studies, and there is a movement to introduce it into the actual process.

However, there are problems to be solved in the chemically amplified resist. First, it is easy to be affected by the atmosphere (air) used. The acid generated in the resist is deactivated by the alkali gas in the air, the reaction does not proceed and the sensitivity is drastically reduced. In particular, the reaction on the surface of the exposed portion does not proceed, so that the resolution is significantly reduced. Further, the chemically amplified resist is baked after exposure to supply the energy of the catalytic reaction due to the acid, but during this exposure to baking, it is particularly susceptible to the influence of alkali in the atmosphere, which causes the instability of the performance. There is.

In order to solve this, a method of forming a non-polar organic resin film (polyolefin) on a resist to block contact with the atmosphere, and adding an acid to a water-soluble resin (polyvinyl alcohol, etc.) at present. There is a method of applying a substance to block the contact with the atmosphere, supplement the acid on the resist surface portion, and trap the alkali from the atmosphere. However, since the non-polar polymer needs to be peeled off with a non-polar solvent before development, it is troublesome when developing with an alkaline aqueous solution or alcohol.

When a water-soluble resin is used, it can be peeled off with water, an aqueous alkali solution, or alcohol, so that it does not have the drawbacks of non-polar polymers, but the acid causes excessive reaction on the resist surface, resulting in a reduction in resolution. However, the film loss of the resist itself increases and it is extremely difficult to control. In addition, in order to apply the strongly acidic aqueous solution, it is necessary to take measures against strong acid in the factory where the pattern forming process is performed. For example, applicators, storage bottles, drain hoses, etc., but their countermeasures must be quite expensive. In addition, the influence of acid on the elements and wiring materials is also a concern. However, the amount of acid added cannot be reduced. This is because most water-soluble resins such as polyvinyl alcohol are almost neutral resins, and alkali in the air easily penetrates if the amount of acid added is reduced.

The above-mentioned problems are related to photolithography in which the atmosphere is often in contact with the resist, and tend to be considered to be unrelated to the charged radiation such as electron beam or ion beam which is exposed in vacuum. However, in reality, the exposure causes the resist surface to have a high temperature and volatilizes the acid on the resist surface in a vacuum, so that the reaction of the resist surface portion does not proceed and the sensitivity and resolution deteriorate. In addition, contact with the atmosphere is inevitable during baking after exposure. That is,
When using charged radiation, a resist protective film is essential in order to prevent invasion of alkali in the atmosphere and volatilization of acid from the resist, but there is currently no suitable protective film.

In the case of charged radiation, there is another circumstance to be considered. It is the charging of the resist. When the resist is exposed to an electron beam, electrons accumulate there and are negatively charged. Therefore, the subsequently irradiated electron beam is twisted and bent, and a pattern shift occurs. In order to prevent this, it is necessary to apply a conductive agent. If the conductive agent has the above-mentioned effect of blocking the atmosphere, it is exactly two birds with one stone. On the contrary, when it becomes necessary to apply a coating film for blocking the atmosphere in addition to the conductive agent, this increases labor and leads to an increase in cost.

However, among the currently known conductive agents,
First, since the solvent using the TCNQ complex is an organic solvent, the resist dissolves when applied and cannot be used. There are polythiophene-based and sulfonated polyaniline-based conductive agents that are water-soluble and do not have such concerns. The polythiophene-based conductive agent is sold as "Espacer" by Showa Denko KK. However, it is too acidic (pH 2 or less) and has the same drawbacks as the acid-added water-soluble resin described above.

The sulfonated polyaniline-based conductive agent deeply related to the present invention is a sample based on Japanese Patent Application No. 04-157953. It is alkaline in a liquid state, and extra alkaline volatilizes in a film state to become weakly acidic. . Therefore, it is an excellent material that does not require measures against strong acids in the factory. (Because alkali development is used for a long time in the resist process,
Alkaline measures are not particularly required). However, when this is applied to a chemically amplified resist, a drastic decrease in sensitivity and a decrease in resolution are observed. This is because the alkali in the liquid state strongly adsorbs to the resist to deactivate the generated acid, and the acidity in the film state is weak so that the effect of replenishing the acid on the resist surface part and the alkali trap in the atmosphere is low. It is believed that there is. However, in order to use the sulfonated polyaniline, which is a conductive resin, as an aqueous solution, it is necessary to add a considerable amount of alkali to the solution in order to increase the solubility in water, which is difficult to reduce.

[0010]

Therefore, in the present invention, when a chemically amplified resist is exposed to charged radiation to form a pattern, deactivation of an acid generated after the chemically amplified resist is exposed and the resist is prevented. An object of the present invention is to provide a composition for forming a conductive agent that can be used to prevent charging (charge-up) due to charged particles on the surface, and a pattern forming method using the composition.

[0011]

According to the present invention, the above-mentioned problems are as follows: (a) The content of sulfone groups is 20 to 80 relative to the aromatic ring.
% Sulfonated polyaniline 0.1-20 parts by weight, (b) 100 parts by weight of solvent, (c) amines and / or quaternary ammonium salt 0.01
10 to 10 parts by weight of (d) at least one sulfone group-containing component selected from the following (A) and (B) (A) sulfone group-containing compound (B) sulfone group-containing polymer: It is solved by using a composition characterized in that it comprises 0.001 to 100 parts by weight.

The sulfonated polyaniline of the component (a) constituting the composition used in the present invention can be prepared by
1985, 1124, JP-A 61-197633, JP-A 01-301714, J. Am. Ch
em. Soc. , 1991, 113, 2665-266
6. J. Am. Chem. Soc. , 1990, 11
2,2800. , WO9106887 and USP509
Various sulfonated polyanilines described in 3439 can be used. In addition, although compounds obtained by various other synthetic methods can be used, at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines;
Sulfonated polyanilines (described in JP-A-5-178989) copolymerized with-, m- or / and p-aminobenzenesulfonic acids and further sulfonated with a sulfonating agent, aniline, N-alkylaniline and phenylene Aniline-based conductive polymers having a sulfone group obtained by copolymerizing at least one compound selected from the group consisting of diamines with an aminobenzenesulfonic acid substituted with an alkoxy group (described in Japanese Patent Application No. 5-48540).
Etc. are preferably used.

These (a) sulfonated polyanilines are represented by the general formula shown in the following formula (1).

[0014]

[Chemical 1]

(In the above formula (1), R ₁ , R ₂ , R ₃ and R
₄ , R ₅ , R ₆ , R ₇ or R ₈ each represent hydrogen, a sulfone group, an alkyl group (having 1 to 4 carbon atoms) or an alkoxy group (having 1 to 4 carbon atoms), and R ′ represents hydrogen or the number of carbon atoms. 1
To 4 alkyl groups, benzenesulfonic acid groups or benzenecarboxylic acid groups, and x represents an arbitrary number of 0 <x <1. The content of the sulfo group of (a) used is preferably in the range of 20 to 80% with respect to the aromatic ring, and the molecular weight thereof is preferably 300 to 500,000, more preferably 500 to 100,000. When the sulfo group content is less than 20%, sufficient conductivity cannot be obtained, and when it is more than 80%, the solubility in a solvent is deteriorated. If the molecular weight is less than 300, the wettability at the time of application is poor, and if it is 500,000 or more, the solubility is low.

The proportion of the sulfonated polyaniline component (a) used is 0.001 to 100 parts by weight, preferably 0.0 to 100 parts by weight of the solvent (b), as described above.
It is 2 to 50 parts by weight. The ratio of the component (a) is 0.00
If the amount is less than 1 part by weight, pinholes are generated in the film or the conductivity is inferior, whereas if it exceeds 100 parts by weight, phenomena such as solubility, flatness deterioration and gelation of the polymer are observed.

The component (b) solvent may be water alone or a mixture of water and an organic solvent. As the organic solvent to be mixed, alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone and methyl isobutyl ketone, cellosolves such as methyl cellosolve, ethyl cellosolve and ethyl cellosolve acetate, methyl propylene glycol, ethyl propylene glycol. Propylene glycols such as and the like are preferably used. These are used by mixing with water at an arbitrary ratio, but are preferably used in the range of 0 to 100 parts by weight with respect to 100 parts by weight of water.

Further, as the component (c) amines and / or quaternary ammonium salts of the composition used in the present invention, compounds represented by the formulas (2) and (3) are used. The structures of the amines used are shown in formula (2).

[0019]

[Chemical 2]

(In the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ O
H, CH ₂ CH ₂ OH, CONH ₂ or NH ₂ . ) Next, the structural formula of the quaternary ammonium salt used is shown in Formula (3).

[0021]

[Chemical 3]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and X ⁻ is OH ⁻ , 1 / 2SO ₄ ^2−. , NO ₃ ^-,
1 / 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 (COO) ₂ ²⁻ or R′COO ⁻ (wherein R ′ is an alkyl group having 1 to 3 carbon atoms). ) The proportion of the component (c) amines and / or quaternary ammonium salts used is as described above in (b) solvent 10
It is 0.01 to 10 parts by weight, preferably 0.2 to 10 parts by weight, relative to 0 parts by weight. The ratio of the component (c) is 0.
If it is less than 01 parts by weight, the solubility of the component (a) is not sufficient,
On the other hand, if the amount exceeds 10 parts by weight, the solution exhibits strong basicity, and adverse effects such as a decrease in conductivity, a drastic decrease in resist sensitivity, and a decrease in resolution occur. The pH of the solution can be arbitrarily adjusted by the concentration, type and mixing ratio of amines and / or quaternary ammonium salts, and can be used in the range of pH 5-12.

As the component (d), at least one compound selected from the following (A) low molecular weight compound containing a sulfone group and (B) a polymer containing a sulfone group is used. The (A) sulfone group-containing compound is not particularly limited as long as it is a compound having a sulfone group in the molecule, but is not limited to benzenesulfonic acid, alkoxy-substituted benzenesulfonic acid, alkylbenzenesulfonic acid, alkylsulfonic acid, α-olefinalkyl. Sulfonic acid, alkylnaphthalenesulfonic acid, alkylsulfoacetic acid and salts thereof are preferably used, and ammonium salt is particularly preferably used. Here, the alkyl group has 1 to 2 carbon atoms.
4 is preferable and a C3-C18 is more preferable. Also,
The alkoxy group preferably has 1 to 18 carbon atoms, and has 3 carbon atoms.
-12 are more preferable.

As the ammonium salt, the compound of formula (4) is preferably used.

[0025]

[Chemical 4]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.) (B) A polymer containing a sulfone group , A polymer having at least 10% or more of repeating units containing a sulfone group. That is, a polymer of at least one kind of monomer selected from the group of monomers containing a sulfone group, or two or more kinds of monomers selected from each of a monomer group containing a sulfone group and a monomer group not containing a sulfone group. It means a copolymer consisting of.

A more specific description will be given below. The monomer having a sulfone group is not particularly limited as long as it has a sulfone group in the molecule, but is not limited to vinylbenzenesulfonic acid such as vinylbenzenesulfonic acid and allylbenzenesulfonic acid, and sulfone such as allylsulfonic acid and methacrylsulfonic acid. Olefins, 2
-N-sulfoalkyl acrylamides such as acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-dodencansulfonic acid, 4-acrylamidobenzenesulfonic acid, 2-methacrylamidopropanesulfonic acid ,
N such as 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-n-dodencansulfonic acid, and 4-methacrylamidobenzenesulfonic acid.
-Sulfoalkyl methacrylamides, 4-sulfophenyl acrylate, 3-sulfopropyl acrylate,
Acrylic esters such as 2-sulfo-2-methylpropyl acrylate and 2-hydroxy-3-sulfopropyl acrylate, 4-sulfophenyl methacrylate, 3-sulfopropyl methacrylate, 2-sulfo-
2-methylpropyl methacrylate, 2-hydroxy-
Methacrylic acid esters such as 3-sulfopropyl methacrylate and 2-sulfoethyl methacrylate and salts thereof are particularly preferably used.

Further, the monomer containing no sulfone group is not particularly limited as long as it has a double bond copolymerizable with the above-mentioned monomer, but acrylic acid such as methyl acrylate, butyl acrylate, hexyl acrylate, dodecyl acrylate, etc. Esters, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, dodecyl methacrylate, acrylic acid and methacrylic acid such as acrylic acid, methacrylic acid, 2-butylacrylic acid, styrene, α-methylstyrene Such as styrene, acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, etc. Riruamido and methacrylamides, acrylonitrile, methacrylonitrile, 2
-Acrylonitrile such as ethyl acrylonitrile and methacrylonitriles are preferably used.

The monomers are used by polymerizing each alone, or by copolymerizing two or more kinds of monomers. Alternatively, a copolymer obtained by copolymerizing at least two kinds of monomers selected from each of the group of monomers and the group of monomers can be used. Both of acid type and salt type are used as the sulfo group of these copolymers, and ammonium salt is particularly preferable. As the ammonium salt, the compound of formula (4) is preferably used.

The proportion of the group of monomers is preferably at least 10%, more preferably 2%.
It is preferable to contain 0% or more. Further, the molecular weight of (B) is preferably 300 to 200,000, and 500 to 10
Thousands are more preferable. As described above, the proportion of the component (d) used is 0.001 with respect to 100 parts by weight of the solvent (b).
To 100 parts by weight, preferably 0.02 to 50 parts by weight, more preferably 0.1 to 10 parts by weight. Ingredient (d)
If the ratio is less than 0.001, the acid trapping effect is not sufficient, and if it exceeds 100 parts by weight, the contrast decreases.

The pH of the composition is 5-12, preferably 7-1.
It is 0. If the pH is less than 5, the resist surface portion reacts to lower the contrast, and if it exceeds 12 the acid generated in the resist is deactivated and the sensitivity is lowered. Further, the composition of the present invention comprises
If necessary, a surfactant, a storage stabilizer, an adhesion aid and the like can be added.

The above is the composition of the conductive agent applied on the resist. In order to sufficiently bring out the effect of improving the sensitivity and resolution of the chemically amplified resist as the resist protective film, (2) the chemically amplified type is used. It has been found that a high temperature bake after resist application and a high temperature bake after application of the sulfonated polyaniline composition (conductive agent forming composition) are important.

Thus, according to the present invention, the chemically amplified resist is applied at 110 ° C. or higher, more preferably 120 ° C.
Baking is performed at the above temperature, the sulfonated polyaniline composition for forming a conductive agent is applied thereon, and baking is further performed at a temperature of 110 ° C. or higher, more preferably 120 ° C. or higher to form a conductive agent layer on the resist. And then irradiated with charged radiation, especially an electron beam or a focused ion beam,
Then, there is provided a pattern forming method including a step of developing with an alkaline aqueous solution or alcohol.

The high temperature baking of the resist makes the resist film dense and makes it difficult for the alkali in the sulfonated polyaniline solution to enter. Also, complete removal of the solvent is important for preventing alkali invasion. By applying a sulfonated polyaniline solution to this and baking at high temperature, the alkali in the sulfonated polyaniline solution is completely removed, and the sulfonated polyaniline containing the sulfone group-containing component remains. This film is dense due to high temperature baking and has a high effect of blocking the atmosphere. In addition, the sulfone group-containing component in the sulfonated polyaniline traps the alkali that is about to enter from the atmosphere.

As described above, this sulfonated polyaniline has an excellent effect as an antistatic agent, and an antistatic effect and an alkali blocking effect can be obtained at the same time. The present invention is effective for both negative and positive types as long as it is a chemically amplified resist, and the type is not particularly limited. However, it is particularly effective for positive type. The composition of the chemically amplified resist is generally composed of a base resin, a cross-linking agent and an acid generator, and the negative type in which the acid generated by exposure acts as a catalyst to promote cross-linking and the base resin There is a positive type which comprises an acid generator and an acid generated by exposure to act as a catalyst to decompose the base resin and make it soluble in a developing solution. Typical examples of such chemically amplified resists are SPIE, Vo
l.923, Electron-Beam, X-rag, and Ion-Beam Technolo
gy: Submicrometer Lithographies VII, 1988, p158-1
71 (negative type), and SPIE, Vol.1086, Advances in Re
sist Technology and Processing VI (1989) p.2-10 (positive type).

In a preferred embodiment of the present invention, a chemically amplified resist containing a copolymer of tertiarybutoxycarbonyloxystyrene and hydroxystyrene represented by the following formula is used.

[0037]

[Chemical 5]

In the case of a resist using the copolymer of tertiary butoxycarbonyloxystyrene and hydroxystyrene, if the resist or the sulfonated polyaniline is baked at less than 110 ° C., a decrease in resist sensitivity and a decrease in resolution are observed. It Therefore, when using this resist, it is desirable to bake at 110 ° C. or higher, more preferably 120 ° C. or higher. In the case of this resist, 130
Since a remarkable deterioration of the resolution is observed as early as at 0 ° C (it is considered that the tertiary butoxycarbonyloxy group is cleaved by heat), baking at 115 to 125 ° C is most desirable.

The copolymerization ratio of tertiary butoxycarbonyloxystyrene and hydroxystyrene is 1: 19-.
It is preferably between 1: 1 and particularly preferably between 1: 9 and 3: 7. If the amount of tertiary butoxycarbonyloxystyrene is less than 1:19, the film thickness is reduced due to development, and the contrast of the resist is lowered.
On the other hand, if it is higher than 1: 1, a negative image tends to occur, and the contrast also deteriorates. At this time, the sulfone group-containing component (d) contained in the conductive agent has 3 carbon atoms in the alkyl group regardless of whether it is an alkylbenzenesulfonic acid or an alkylsulfonic acid.
It is desirable that the number is 20 or less. The acid concentration is particularly preferably between 0.001 and 0.1 part with respect to 100 parts of solvent.

The baking described here means baking for evaporating the solvent after coating the resist and after coating the sulfonated polyaniline to solidify the film, and after the acid is generated by exposure, the baking is performed to accelerate the reaction. Please note that is not included. In the present invention, the temperature of the post-exposure bake is not specified at all, and the temperature having the best resist sensitivity and resolution can be freely selected. Exposure and development can be performed by a conventional method.

[0041]

【Example】

EXAMPLE 1 tert-butoxycarbonyl oxystyrene: hydroxystyrene = 2: copolymer of 8 (Mw of about 5,000) 1 g triphenyl sulfonium triflate ^{_{(Ph 3 S + CF 3 SO}} 3 -) 0 A resist prepared by dissolving 0.05 g of ethyl lactate in 6 g of ethyl lactate was applied on a silicon wafer to a thickness of 0.6 μm.

After that, the resist was pre-baked for 2 minutes, further, a sulfonated polyaniline solution was applied so as to have a thickness of 0.05 μm, and further baked for 1 minute to obtain a sample. The composition of the sulfonated polyaniline solution is as follows: sulfonated polyaniline (sulfone group content is 40% relative to aromatic ring) ... 5 parts Water (solvent) ... 100 parts Dimethylethylamine ... 5 parts Dodecylbenzenesulfonic acid ... Resist shown in the table Was exposed to an electron beam and immediately baked at 90 ° C. for 2 minutes and developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute. The pattern thus produced was observed with an electron microscope to determine the resolution. Some of the data are shown below.

[0043]

[Table 1]

From the above data, a temperature of 110 ° C. or higher is suitable for both the resist and the baking of sulfonated polyaniline. There is an optimum value for the amount of acid added. And so on. From this, it can be seen that it is important to extract the optimum value of the baking temperature. After exposure, it was left in the atmosphere for 1 hour, but both sensitivity and resolution were stable and did not change. From this, it is understood that the sulfonated polyaniline film protects the resist and prevents the invasion of alkali in the atmosphere.

The same evaluation was carried out using a resin having a sulfo group content of 15% of sulfonated polyaniline, but the sensitivity and resolution of the resist were improved, but the conductivity was very low and the film was used as an antistatic film. It turned out to be a useless level. Further, in the case of a resin having a sulfone group content of 90%, the uniformity of the film at the time of coating was extremely poor, and the solubility in the solvent was originally considered to be poor.

When dimethylethylamine was not added, the coatability of the conductive film was poor, and when 20 parts were added, the alkali removal by baking did not proceed sufficiently and the resolution was extremely low. [Example 2] The composition of the sulfonated polyaniline solution was evaluated as in Example 1 as follows. Sulfonated polyaniline (sulfone group content is 60% based on aromatic ring) ... 5 parts Water (solvent) ... 100 parts Dimethylethylamine ... 5 parts Poly-2-acrylamidopropanesulfonic acid (average molecular weight 6,400) ... Show

[0047]

[Table 2]

It can be seen that a temperature of 110 ° C. or higher is suitable for both resist and bake of sulfonated polyaniline. After exposure, the sample was allowed to stand in the atmosphere for 1 hour, but both sensitivity and resolution were stable and did not change. From the above, it was found that sulfonated polyaniline containing a polymer containing a sulfone group can also be used. [Example 3] The composition of the sulfonated polyaniline solution was evaluated as in Example 1 as follows. Sulfonated polyaniline (sulfone group content is 60% relative to aromatic ring) ... 5 parts Water (solvent) ... 100 parts Dimethylethylamine acetate ... 5 parts Dodecylbenzenesulfonic acid ... 5 parts As a result, the baking temperature is 110 ° C. or higher. , A high resolution was obtained, and 0.2 μml / s was resolved with a good shape. From this, it is understood that the sulfonated polyaniline added with a quaternary ammonium salt can also be used.

Some of the data examined for the negative type are also shown below. [Example 4] Negative resist SAL-60 manufactured by Shipley Co., Ltd.
As for Example 1, the composition of the sulfonated polyaniline solution was evaluated as in Example 1 as follows. Sulfonated polyaniline (sulfone group content is 60% based on aromatic ring) ... 5 parts Water (solvent) ... 100 parts Dimethylethylamine ... 5 parts Poly-2-acrylamidopropanesulfonic acid (average molecular weight 6,400) ... 5 parts As a result, it was found that the highest resolution was obtained when the baking temperature was 120 to 140 ° C. Further, the shape of the pattern becomes closer to a rectangle as compared with the case where sulfonated polyaniline containing no sulfo group-containing component is applied. After exposure, the film was left in the atmosphere for 1 hour, but the sensitivity and resolution were stable and did not change. From this, it was found that the application of the conductive agent according to the present invention is also effective for the chemically amplified negative resist.

[0050]

According to the present invention, when a chemically amplified resist is exposed to charged radiation, a suitable conductive agent layer is formed on the resist, and the resist and conductive agent forming layer are baked at a high temperature. It is possible to form a high-resolution pattern because the positional deviation of the pattern due to charging is prevented and the resist is not deactivated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 81/06 LRF G03F 7/004 501 7/038 505 7/039 501 7/11 501 7/38 501 H01L 21/027 7352-4M H01L 21/30 575 (72) Inventor Keiji Watanabe 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor Miwa Igarashi 1015, Uedaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Address within Fujitsu Limited (72) Inventor Yoko Mitsuko 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Within Fujitsu Limited (72) Takashi Maruyama 1015, Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Within Fujitsu Limited (72) Inventor Keiko Yano 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Fujitsu Limited (72) Inventor Tomomi Nakamura O 10-10 Daikoku-cho, Tsurumi-ku, Yokohama-shi, Kanagawa Nitto Chemical Industry Co., Ltd. (72) Inventor Shigeru Shimizu 10-1 Daikoku-cho, Tsurumi-ku, Yokohama City, Kanagawa Prefecture (72) Invention Person Takashi Saito 10-1 Daikokucho, Tsurumi-ku, Yokohama-shi, Kanagawa Nitto Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A sulfonated polyaniline having a content of (a) sulfone groups of 20 to 80% with respect to an aromatic ring.
20 parts by weight, (b) 100 parts by weight of solvent, (c) 0.01 amines and / or quaternary ammonium salt 0.01
10 to 10 parts by weight of (d) at least one sulfone group-containing component selected from the following (A) and (B) (A) sulfone group-containing compound (B) sulfone group-containing polymer A conductive agent-forming composition comprising 0.001 to 100 parts by weight. 2. The conductive agent-forming composition according to claim 1, wherein the sulfone group-containing component is an ammonium salt. 3. A chemically amplified resist is applied, then baked at a temperature of 110 ° C. or higher, the composition of claim 1 or 2 is applied thereon, and further baked at a temperature of 110 ° C. or higher, and then charged. A pattern forming method comprising a step of irradiating with radiation and then developing with an aqueous alkali solution or alcohol. 4. The pattern forming method according to claim 3, wherein a chemically amplified resist containing a copolymer of tertiary oxybutoxycarbonyloxystyrene and hydroxystyrene is used. 5. The pattern forming method according to claim 4, wherein a polymerization ratio of tertiarybutoxycarbonyloxystyrene and hydroxystyrene of the copolymer is within a range of 1:19 to 1: 1.