JP4616040B2 - Resist cover film forming material, resist pattern forming method, electronic device and manufacturing method thereof - Google Patents

Description

The present invention provides an immersion exposure technique that realizes improvement in resolution by filling a medium (liquid) having a refractive index n larger than 1 (refractive index of air) between a projection lens of an exposure apparatus and a wafer. Resist cover film forming material that can be suitably used as a resist cover film for immersion exposure that protects a resist film from liquid and has high transmittance for ArF excimer laser light and F ₂ excimer laser light, and a resist pattern using the same And a method of manufacturing the electronic device.

In recent years, with the progress of high integration of semiconductor integrated circuits, the minimum pattern size has reached a region of 100 nm or less. Conventionally, a fine pattern is formed by coating a processed substrate on which a thin film is formed with a resist film, performing selective exposure, and developing to form a resist pattern, and dry etching using the resist pattern as a mask. And then removing the resist pattern to obtain a desired pattern.
In order to miniaturize the pattern, it is required to shorten the wavelength of the exposure light source and to develop a resist material having a high resolution according to the characteristics of the light source. However, there is a problem that it takes a huge cost to improve the exposure apparatus aiming at shortening the wavelength of the exposure light source. In recent years, KrF (krypton fluoride) excimer laser light (wavelength) which has been used conventionally has been problematic. Although ArF (argon fluoride) excimer laser light (wavelength: 193 nm) has been put into practical use as next-generation exposure light instead of 248 nm), an ArF excimer laser exposure apparatus has begun to be marketed, but it is still very expensive. In addition, it is not easy to develop a resist material corresponding to the short wavelength exposure, and a resist material effective for short wavelength exposure has not been proposed yet. For this reason, it has been difficult to realize pattern miniaturization by conventional resist pattern forming methods.

  Therefore, the immersion exposure method has attracted attention as the latest exposure technique. According to the immersion exposure method, the resolution can be improved by filling a medium (liquid) having a refractive index n larger than 1 (the refractive index of air) between the projection lens of the stepper and the wafer. it can. Usually, the resolution of the stepper is expressed by the following equation: resolution = k (coefficient) × λ (light source wavelength) / NA (numerical aperture), where the light source wavelength λ is shorter and the numerical aperture NA of the projection lens is larger, High resolution can be obtained. Here, NA is expressed by the following equation, NA = n × sin α, where n is the refractive index of the medium through which the exposure light passes, and α is the angle formed by the exposure light. Since the exposure in the conventional pattern formation method is performed in the atmosphere, the refractive index n is 1, but in the immersion exposure method, a liquid having a refractive index n greater than 1 is interposed between the projection lens and the wafer. use. Therefore, in the numerical aperture NA equation, n is increased, and the minimum resolution dimension can be reduced to 1 / n at the same incident light incident angle α. Moreover, with the same numerical aperture NA, there is an advantage that α can be reduced and the depth of focus can be increased n times.

  The immersion technique using a liquid having a refractive index larger than the refractive index of air is an existing technique in the field of microscopes. An exposure apparatus (see Patent Document 1) that exposes with a liquid having a refractive index that is substantially equal to or slightly smaller than the refractive index of the lens in between is proposed. It has been in the last few years that the study began. For this reason, inconveniences related to the immersion exposure apparatus and the resist material used therefor are gradually becoming clear.

The problem is that the resist film is exposed to a liquid (for example, water) filled between the projection lens and the wafer, so that an acid component generated in the resist film at the time of exposure oozes out into the water. Reducing the sensitivity of the resist. Also, when excimer laser light is irradiated with water penetrating into the resist film, some chemical reaction occurs, the original performance of the resist is impaired, or the projection lens of the exposure apparatus is soiled by degassing. Can be mentioned. The contamination of the lens has a problem of causing poor exposure and lowering the resolution.
In order to prevent these problems, although a method of forming a resist cover film on the upper surface of the resist film has been studied, the resist cover film is not dissolved without being mixed with the resist film. It is difficult to form by coating. In addition, the ArF excimer laser light having a wavelength of 193 nm and the F ₂ excimer laser light having a shorter wavelength (157 nm) than the ArF excimer laser light do not transmit ordinary organic substances, and therefore can be used as a resist cover film. The selection range of the resist cover film is extremely narrow, and even if a material that can be used for the resist cover film can be selected, it does not dissolve in the alkaline developer usually used for development. It must be used to remove the resist cover film.

Therefore, the resist film can be formed without dissolving it, and the resist film is effectively protected from the liquid having a high refractive index so that the original resist performance is not impaired, and the ArF excimer laser light and the F _2. Currently, no material that can be used for a resist cover film for immersion exposure, which has a high transmittance with respect to excimer laser light and can be easily removed, and a related technology using the material have not been developed. Therefore, development of such technology is desired.

JP 62-066526 A

An object of the present invention is to solve the conventional problems and achieve the following objects. That is,
The present invention provides an immersion exposure technique that realizes improvement in resolution by filling a medium (liquid) having a refractive index n larger than 1 (refractive index of air) between a projection lens of an exposure apparatus and a wafer. An object of the present invention is to provide a resist cover film forming material that can be suitably used for a resist cover film for immersion exposure that protects a resist film from a liquid and has high transmittance for ArF excimer laser light and F ₂ excimer laser light. To do.
Further, the present invention effectively protects the resist film from the liquid and can perform high-definition exposure by liquid immersion exposure without impairing the function of the resist film, thereby forming a fine and high-definition resist pattern. An object of the present invention is to provide a resist pattern forming method that can be easily and efficiently formed.
Further, according to the present invention, it is possible to form a fine and high-definition resist pattern by immersion exposure without impairing the function of the resist film, and a high-performance having a fine wiring pattern formed using the resist pattern. An object is to provide an electronic device manufacturing method capable of efficiently mass-producing electronic devices, and an electronic device such as a high-performance semiconductor device manufactured by the electronic device manufacturing method and having a fine wiring pattern. To do.

As a result of intensive studies in view of the above problems, the present inventor has obtained the following knowledge. That is, in the immersion exposure technique, when a composition containing at least a silicon-containing polymer having an alkali-soluble group and an organic solvent capable of dissolving the silicon-containing polymer is used as a resist cover film forming material, the resist film is dissolved. The ArF excimer laser can be formed on the resist film without any loss and effectively protects the resist film from the high refractive index liquid filled between the projection lens and the wafer. This is a finding that a resist cover film having a high transmittance with respect to light and F ₂ excimer laser light and that can be easily removed can be obtained.

The present invention is based on the above knowledge of the present inventor, and means for solving the problems are as described in (Appendix 1) to (Appendix 17) described later. That is,
The resist cover film forming material of the present invention is used to form a resist cover film that covers the resist film when immersion exposure is performed on the resist film, and has at least an alkali-soluble group and has the following general formula ( At least one selected from silicon-containing polymers represented by 1) to (3) and at least an organic solvent capable of dissolving the silicon-containing polymer. Therefore, in the resist cover film formed using the resist cover film forming material, the resist film is effectively protected from the high refractive index liquid filled between the projection lens and the wafer, and the original resist performance The transmittance with respect to ArF excimer laser light or F ₂ excimer laser light is high and can be easily removed.

ただし、前記一般式（１）中、Ｒ^１はアルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^２は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ａ、ｂ及びｃは比を表し、それぞれａ＞０、ｂ＞０、ｃ≧０である。

In the general formula (1), R ¹ represents at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, R ² represents a monovalent organic group, a triorganosilyl group, and It represents at least one of hydroxyl groups. a, b, and c represent ratios, where a> 0, b> 0, and c ≧ 0, respectively.

ただし、前記一般式（２）中、Ｒ^３及びＲ^４の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^５は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｄ、ｅ及びｆは比を表し、それぞれｄ＞０、ｅ≧０、ｆ≧０である。

However, in the general formula (2), at least one of R ³ and R ^{4 represents} at least one of a monovalent organic group and a triorganosilyl group having an alkali-soluble group, and R ⁵ is a monovalent organic group. Represents at least one of a group, a triorganosilyl group, and a hydroxyl group. d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively.

ただし、前記一般式（３）中、Ｒ^６、Ｒ^７及びＲ^８の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^９は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｇ、ｈ及びｉは比を表し、それぞれｇ＞０、ｈ≧０、ｉ≧０である。

However, in the general formula (3), at least one of R ⁶ , R ⁷ and R ^{8 represents} at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, and R ⁹ is one. It represents at least one of a valent organic group, a triorganosilyl group, and a hydroxyl group. g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively.

In the method for forming a resist pattern of the present invention, after forming a resist film on a substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material of the present invention, and the resist cover film Then, the resist film is irradiated with exposure light by immersion exposure and developed.
In the resist pattern forming method, after forming a resist film on the substrate to be processed, the resist cover film using the resist cover film forming material of the present invention is formed on the resist film. Since the resist cover film is formed of the resist cover film forming material of the present invention, the resist cover film is formed on the resist film without dissolving the resist film. The resist film is exposed to the exposure light by the immersion exposure through the resist cover film. Since the resist cover film is formed of the resist cover film forming material, the resist film is effectively protected from the high refractive index liquid filled between the projection lens and the wafer, and the original resist performance is impaired. I can't. In addition, since the transmittance for ArF excimer laser light and F ₂ excimer laser light is high, the exposure is performed with high definition. It is then developed. Since the resist cover film made of the resist cover film forming material can be easily removed with a normal developer used in the development, it is removed simultaneously with the resist film during the development. As a result, a resist pattern is easily and efficiently formed. The resist pattern thus obtained is fine and high-definition because exposure is performed with high definition without impairing the function of the resist film.

In the method for manufacturing an electronic device of the present invention, after forming a resist film on a substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material of the present invention, and the resist cover film A resist pattern forming step of forming a resist pattern by irradiating the resist film with immersion light by immersion exposure and developing, and patterning the substrate to be processed by etching using the resist pattern as a mask And a process.
In the electronic device manufacturing method, first, in the resist pattern forming step, the resist film is formed on the surface to be processed, which is a target for forming a pattern such as a wiring pattern, and then the resist film is formed on the resist film. A resist cover film using the resist cover film forming material is formed. Since the resist cover film is formed of the resist cover film forming material of the present invention, the resist cover film is formed on the resist film without dissolving the resist film. The resist film is exposed to the exposure light by the immersion exposure through the resist cover film. Since the resist cover film is formed of the resist cover film forming material, the resist film is effectively protected from the high refractive index liquid filled between the projection lens and the wafer, and the original resist performance is improved. Suppresses damage. In addition, since the transmittance for ArF excimer laser light and F ₂ excimer laser light is high, the exposure is performed with high definition. It is then developed. Since the resist cover film made of the resist cover film forming material can be easily removed with a normal developer used in the development, it is removed simultaneously with the resist film during the development. As a result, a resist pattern can be formed with high definition simply and efficiently.
Next, in the patterning step, etching is performed using the resist pattern formed in the resist pattern forming step, so that the surface to be processed is patterned finely and with high definition and with high dimensional accuracy. In addition, a high-quality and high-performance electronic device such as a semiconductor device having a pattern such as a wiring pattern having excellent dimensional accuracy is efficiently manufactured.
The electronic device of the present invention is manufactured by the method for manufacturing an electronic device of the present invention. The electronic device has a pattern such as a wiring pattern having extremely fine and high definition and excellent dimensional accuracy, and has high quality and high performance.

According to the present invention, conventional problems can be solved, and the above object can be achieved.
Further, according to the present invention, an immersion exposure technique that realizes an improvement in resolution by filling a medium (liquid) having a refractive index n larger than 1 (the refractive index of air) between the projection lens of the exposure apparatus and the wafer. A resist cover film forming material that can be suitably used for a resist cover film for immersion exposure that protects the resist film from the liquid and that has a high transmittance with respect to ArF excimer laser light and F ₂ excimer laser light. Can do.
In addition, according to the present invention, the resist film can be effectively protected from the liquid, and can be exposed with high definition by immersion exposure without impairing the function of the resist film. It is possible to provide a method for forming a resist pattern that can be easily and efficiently formed.
Further, according to the present invention, it is possible to form a fine and high-definition resist pattern by immersion exposure without impairing the function of the resist film, and a high-performance having a fine wiring pattern formed using the resist pattern. It is possible to provide an electronic device such as a high-performance semiconductor device which is manufactured by an electronic device manufacturing method capable of efficiently mass-producing electronic devices and has a fine wiring pattern and is manufactured by the electronic device manufacturing method.

(Resist cover film forming material)
The resist cover film forming material of the present invention contains at least a silicon-containing polymer having at least an alkali-soluble group and an organic solvent, and further contains other components and the like appropriately selected as necessary.

The resist cover film forming material is not particularly limited as long as it is alkali-soluble and has high solubility in an alkali developer, and can be appropriately selected according to the purpose. For example, 2.38% by mass at 25 ° C. The dissolution rate with respect to an aqueous tetramethylammonium hydroxide (TMAH) solution is preferably 10 to 1,000 nm / sec, and more preferably 50 to 500 nm / sec. When the resist cover film forming material is alkali-soluble, it can be easily removed by dissolving it in an alkali developer together with the resist film during development.
The method for measuring the dissolution rate is not particularly limited, and can be appropriately selected from known methods according to the purpose. For example, the DRM (Dissoution Rate Monitor) method using laser light interference, crystal oscillation For example, a QCM (Quartz Crystal Microbalance) method using a method of measuring a mass change by frequency change by a child is used. Among these, since the resist cover film-forming material exhibits extremely high solubility, the QCM method capable of measuring with higher accuracy is preferable.

-Silicon-containing polymer-
The silicon-containing polymer needs to be at least one selected from polymers having at least an alkali-soluble group and containing silicon and represented by the following general formulas (1) to (3). . Since silicon has a main skeleton structure, the absorbability with respect to ArF excimer laser light having a wavelength of 193 nm and F ₂ excimer laser light having a wavelength of 157 nm is smaller than that of a general organic substance. Even when formed and exposed, a resist pattern can be formed by transmitting these laser beams. In addition, the silicon-containing polymer is originally a highly hydrophobic polymer, and its water permeability is extremely small compared to general organic substances. However, the silicon in the resist cover film forming material of the present invention to which hydrophilicity is imparted is provided. The contained polymer dissolves in a strongly alkaline resist developer, but has low permeability to water. Therefore, resist resist film prevents side reactions caused by elution of acid from the resist film and penetration of liquid into the resist film. Can be suitably used.

ただし、前記一般式（１）中、Ｒ^１はアルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^２は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ａ、ｂ及びｃは比を表し、それぞれａ＞０、ｂ＞０、ｃ≧０である。

In the general formula (1), R ¹ represents at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, R ² represents a monovalent organic group, a triorganosilyl group, and It represents at least one of hydroxyl groups. a, b, and c represent ratios, where a> 0, b> 0, and c ≧ 0, respectively.

ただし、前記一般式（２）中、Ｒ^３及びＲ^４の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^５は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｄ、ｅ及びｆは比を表し、それぞれｄ＞０、ｅ≧０、ｆ≧０である。

However, in the general formula (2), at least one of R ³ and R ^{4 represents} at least one of a monovalent organic group and a triorganosilyl group having an alkali-soluble group, and R ⁵ is a monovalent organic group. Represents at least one of a group, a triorganosilyl group, and a hydroxyl group. d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively.

ただし、前記一般式（３）中、Ｒ^６、Ｒ^７及びＲ^８の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^９は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｇ、ｈ及びｉは比を表し、それぞれｇ＞０、ｈ≧０、ｉ≧０である。

However, in the general formula (3), at least one of R ⁶ , R ⁷ and R ^{8 represents} at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, and R ⁹ is one. It represents at least one of a valent organic group, a triorganosilyl group, and a hydroxyl group. g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively.

The alkali-soluble group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a group containing a carboxylic acid-containing group, a sulfonic acid-containing group, a phenol-containing group, a hexafluorocarbinol-containing group, or the like. Is mentioned. Among these, it is the same as the alkali-soluble group of the acrylic polymer used in the resist material compatible with ArF laser light, and dissolves uniformly without causing peeling or development residue during development using an alkaline developer. And the carboxylic acid containing group is preferable at the point which can be removed with the said resist film.
The carboxylic acid-containing group is not particularly limited as long as it contains a carboxyl group in a part of its structure, and can be appropriately selected according to the purpose. However, the synthesis of the silicon-containing polymer is easy and alkali-soluble. A group represented by the following general formula (4) is preferable in terms of excellent characteristics.

ただし、前記一般式（４）中、ｍは、次式、０≦ｍ≦５、を充たし、１＜ｍ≦３であるのが好ましい。

However, in the general formula (4), m satisfies the following formula, 0 ≦ m ≦ 5, and preferably 1 <m ≦ 3.

In the general formulas (1) to (3), the monovalent organic group represented by R ² , R ⁵ , and R ⁹ is not particularly limited and may be appropriately selected depending on the purpose. , Methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tertiary butyl, cyclobutyl, pentyl, isopentyl, cyclopentyl, etc., linear, branched, or cyclic having 1 to 10 carbon atoms, substituted or substituted Examples thereof include an unsubstituted alkyl group.
The triorganosilyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include linear, branched or cyclic alkyls having 1 to 6 carbon atoms such as methyl and ethyl. Examples thereof include a silyl group having a group.
Among these, the monovalent organic group and the triorganosilyl group preferably have an unbranched linear alkyl group having 1 to 3 carbon atoms.
In the general formulas (1) to (3), a monovalent organic group having an alkali-soluble group represented by R ¹ , R ³ , R ⁴ , and R ^{6 to} R ⁸ , or a triorgano having an alkali-soluble group Examples of the silyl group include the monovalent organic group or the triorganosilyl group having at least one selected from the alkali-soluble groups as a substituent.
Preferable embodiments of the silicon-containing polymer include silicon-containing polymers having a carboxylic acid represented by the following general formulas (5) to (9).

ただし、前記一般式（５）中、Ｒ^２は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ａ、ｂ及びｃは比を表し、それぞれａ＞０、ｂ＞０、ｃ≧０である。ｍは、次式、１＜ｍ≦３、を充たす。

In the general formula (5), R ² is represents a monovalent organic group, triorganosilyl group, and at least one of the hydroxyl groups. a, b, and c represent ratios, where a> 0, b> 0, and c ≧ 0, respectively. m satisfies the following formula, 1 <m ≦ 3.

ただし、前記一般式（６）中、Ｒ^４及びＲ^５は、一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｄ、ｅ及びｆは比を表し、それぞれｄ＞０、ｅ≧０、ｆ≧０である。ｍは、次式、１＜ｍ≦３、を充たす。

In the general formula (6), R ⁴ and R ⁵ represents a monovalent organic group, triorganosilyl group, and at least one of the hydroxyl groups. d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively. m satisfies the following formula, 1 <m ≦ 3.

ただし、前記一般式（７）中、Ｒ^３及びＲ^５は、一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｄ、ｅ及びｆは比を表し、それぞれｄ＞０、ｅ≧０、ｆ≧０である。ｍは、次式、１＜ｍ≦３、を充たす。

In the general formula (7), R ³ and R ⁵ represents a monovalent organic group, triorganosilyl group, and at least one of the hydroxyl groups. d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively. m satisfies the following formula, 1 <m ≦ 3.

ただし、前記一般式（８）中、Ｒ^７、Ｒ^８及びＲ^９は、一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｇ、ｈ及びｉは比を表し、それぞれｇ＞０、ｈ≧０、ｉ≧０である。ｍは、次式、１＜ｍ≦３、を充たす。

However, in said general formula (8), R < ⁷ >, R < ⁸ > and R < ⁹ > represent at least any one of a monovalent organic group, a triorganosilyl group, and a hydroxyl group. g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively. m satisfies the following formula, 1 <m ≦ 3.

ただし、前記一般式（９）中、Ｒ^６、Ｒ^７及びＲ^９は、一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｇ、ｈ及びｉは比を表し、それぞれｇ＞０、ｈ≧０、ｉ≧０である。ｍは、次式、１＜ｍ≦３、を充たす。

However, in said general formula (9), R < ⁶ >, R < ⁷ > and R < ⁹ > represent at least any one of a monovalent organic group, a triorganosilyl group, and a hydroxyl group. g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively. m satisfies the following formula, 1 <m ≦ 3.

In the general formulas (5) to (9), the monovalent organic group represented by R ^{1 to} R ⁹ is preferably an alkyl group having 1 to 5 carbon atoms, and as the triorganosilyl group, A trialkylsilyl group having an alkyl group having 1 to 5 carbon atoms is preferred. If the alkyl group has 6 or more carbon atoms, the glass transition temperature (Tg) of the silicon-containing polymer may be low, and a resist cover film may not be formed.

The weight average molecular weight of the silicon-containing polymer having at least the alkali-soluble group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is 1,000 to 1,000,000 in terms of polystyrene. Preferably, 2,000-100,000 is more preferable.
When the weight average molecular weight is less than 1,000, the heat resistance may be lowered, and when it exceeds 1,000,000, the coatability may be lowered.
The weight average molecular weight can be measured, for example, by a GPC (Gel Permeation Chromatography) method, which is a kind of liquid chromatography technique, in which separation is performed based on a difference in molecular size.

  The content of the silicon-containing polymer having at least the alkali-soluble group in the resist cover film forming material is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, 1-5 mass% is more preferable. If the content is less than 0.1% by mass, the film forming property may be inferior, such as pinholes. If the content exceeds 20% by mass, the loss of light source light transmittance increases, Resolution may be reduced.

-Organic solvent-
The organic solvent is not particularly limited as long as it can dissolve the silicon-containing polymer, and can be appropriately selected according to the purpose, but preferably does not dissolve the resist film, for example, a fatty acid having 3 or more carbon atoms. An aliphatic alkanol having 4 or more carbon atoms is more preferable. When the carbon number is 2 or less, the solubility of the silicon-containing polymer may be lowered.
The aliphatic alkanol having 3 or more carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include n-butyl alcohol and isobutyl alcohol. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content in the said resist cover film forming material of the said organic solvent, According to the objective, it can select suitably.

-Other ingredients-
The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected according to the purpose. Examples thereof include various known additives. For example, for the purpose of improving coatability. In some cases, a surfactant can be added.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, nonionic surfactants are preferable in that they do not contain metal ions.

The nonionic surfactant is preferably selected from an alkoxylate surfactant, a fatty acid ester surfactant, an amide surfactant, an alcohol surfactant, and an ethylenediamine surfactant. Can be mentioned. Specific examples of these include polyoxyethylene-polyoxypropylene condensate compounds, polyoxyalkylene alkyl ether compounds, polyoxyethylene alkyl ether compounds, polyoxyethylene derivative compounds, sorbitan fatty acid ester compounds, glycerin fatty acid ester compounds, Primary alcohol ethoxylate compound, phenol ethoxylate compound, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, Secondary alcohol ethoxylate type and the like.
The cationic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkyl cationic surfactants, amide type quaternary cationic surfactants, and ester type quaternary cationic types. Surfactant etc. are mentioned.
There is no restriction | limiting in particular as said amphoteric surfactant, According to the objective, it can select suitably, For example, an amine oxide type surfactant, a betaine type surfactant, etc. are mentioned.
The content of the surfactant in the resist cover film forming material can be appropriately determined according to the type and content of the silicon-containing polymer having at least the alkali-soluble group, the organic solvent, and the like.

-Use-
The resist cover film-forming material of the present invention is preferably used by coating on a resist film, and the coating method is not particularly limited and can be appropriately selected according to the purpose. For example, spin coating Law.
When the resist cover film forming material is applied onto the resist film, a cover film is formed on the resist film. At this time, since the resist cover film forming material contains an organic solvent capable of dissolving the silicon-containing polymer together with the silicon-containing polymer, the cover film can be formed without dissolving the resist film. . In addition, the silicon-containing polymer is a polymer having a main skeleton structure of silicon, which has lower absorbability with respect to ArF excimer laser light having a wavelength of 193 nm and F ₂ excimer laser light having a wavelength of 157 nm than that of a general organic substance. Therefore, a resist pattern can be formed even when the resist film is applied and exposed. Further, since the silicon-containing polymer has at least the alkali-soluble group, it can be dissolved in an alkali developer, and can be easily removed by dissolving it together with the resist film during development.

The exposure light transmittance of the resist cover film is, for example, preferably 30% or more and more preferably 80% or more when the thickness is 100 nm. If the exposure light transmittance is less than 30%, the exposure light transmittance is small, so that the resist film cannot be exposed with high definition, and a fine and high definition resist pattern cannot be obtained. is there.
As the exposure light is not particularly limited and may be appropriately selected depending on the intended purpose, for example, KrF excimer laser light, ArF excimer laser, F ₂ excimer laser beam, and the like. Among these, ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm) and the like are preferable because they have a short wavelength and can form a high-definition resist pattern.

-Resist film forming material-
The material of the resist film (the resist film to which the resist cover film forming material of the present invention is applied) is not particularly limited and can be appropriately selected from known resist materials according to the purpose. Any of positive types may be used, and examples thereof include KrF resist, ArF resist, and F ₂ resist that can be patterned with a KrF excimer laser, ArF excimer laser, F ₂ excimer laser, and the like. These may be chemically amplified or non-chemically amplified. Among these, a KrF resist, an ArF resist, a resist containing an acrylic resin, and the like are preferable. From the viewpoint of finer patterning, an improvement in throughput, and the like, an ArF resist whose extension of the resolution limit is urgently required. And at least one of resists comprising an acrylic resin is more preferable.
Specific examples of the resist film forming material include novolak resist, PHS resist, acrylic resist, cycloolefin-maleic anhydride (COMA) resist, cycloolefin resist, and hybrid (alicyclic acrylic). -COMA copolymer) resist and the like. These may be modified with fluorine.
The resist film forming method, size, thickness and the like are not particularly limited and can be appropriately selected depending on the purpose. In particular, the thickness is appropriately determined depending on the surface to be processed, etching conditions, and the like. Generally, it is about 0.2 to 200 μm.

  The resist cover film forming material of the present invention is suitable for forming a resist cover film for protecting a resist film from a high refractive index liquid filled between a projection lens of an exposure apparatus and a wafer in immersion exposure technology. Can be used. The resist cover film-forming material of the present invention can be used particularly suitably for the resist pattern forming method of the present invention, the electronic device manufacturing method of the present invention, and the like.

(Method for forming resist pattern)
In the resist pattern forming method of the present invention, after forming a resist film on a substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material of the present invention, and the resist cover is formed. This includes irradiation with exposure light by immersion exposure to the resist film through the film and development, and further includes other processing appropriately selected as necessary.

<Resist film formation process>
The resist film forming step is a step of forming a resist film on the substrate to be processed.
Suitable examples of the material for the resist film include those described above for the resist cover film forming material of the present invention.
The resist film can be formed by a known method such as coating.
The surface to be processed (base material) is not particularly limited and may be appropriately selected depending on the purpose. However, when the resist film is formed on an electronic device such as a semiconductor device, the surface to be processed Examples of (base material) include the surface of a semiconductor base material, and specifically, a substrate such as a silicon wafer, various oxide films, and the like are preferable.

<Resist cover film formation process>
The resist cover film forming step is a step of forming a resist cover film on the resist film using the resist cover film forming material of the present invention.
The resist cover film is preferably formed by coating, and the coating method is not particularly limited and can be appropriately selected from known coating methods according to the purpose. For example, spin coating method Etc. are preferable. In the case of the spin coating method, for example, the rotational speed is about 100 to 10000 rpm, preferably 800 to 5000 rpm, the time is about 1 to 10 minutes, and preferably 1 to 90 seconds.
There is no restriction | limiting in particular as thickness at the time of the said application | coating, Although it can select suitably according to the objective, For example, 10-300 nm is preferable and 50-150 nm is more preferable.
If the thickness is less than 10 nm, defects such as pinholes may occur. If the thickness exceeds 300 nm, the transmittance of ArF excimer laser light or F ₂ excimer laser light is reduced, and resolution and exposure sensitivity are reduced. There are things to do.

  The conditions and method for baking (heating and drying) the applied resist cover film forming material during or after the application are not particularly limited as long as the resist film is not softened, and is appropriately selected according to the purpose. For example, the temperature is preferably about 40 to 150 ° C., more preferably 80 to 120 ° C., and the time is preferably about 10 seconds to 5 minutes, and 30 seconds to 90 seconds. More preferred.

<Immersion exposure process>
The immersion exposure step is a step of irradiating the resist film with exposure light by immersion exposure through the resist cover film.
The immersion exposure can be suitably performed by a known immersion exposure apparatus, and is performed by irradiating the resist film with the exposure light through the resist cover film. Irradiation of the exposure light is performed on a partial area of the resist film, whereby the partial area is cured, and an uncured area other than the cured partial area in a development step described later. The region is removed and a resist pattern is formed.

The liquid used for the immersion exposure and filled between the projection lens of the stepper and the wafer is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the liquid has a refractive index higher than the refractive index (refractive index = 1).
The liquid having a refractive index greater than 1 is not particularly limited and may be appropriately selected depending on the intended purpose. However, the higher the refractive index, the more preferable, for example, oil, glycerin, alcohol, and the like. It is done. Among these, pure water (refractive index = 1.44) is preferable.
There is no restriction | limiting in particular as said exposure light, Although it can select suitably according to the objective, It is preferable that it is short wavelength light, for example, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm) And F ₂ excimer laser light (157 nm). Among these, ArF excimer laser light and F ₂ excimer laser light are preferable in that a high-definition resist pattern can be obtained.

<Development process>
The developing step exposes the resist film through the resist cover film in the liquid immersion exposure step, cures the exposed area of the resist film, and then develops the resist film by removing the uncured area. This is a step of forming a pattern.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.
The developer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the resist cover film formed of the resist cover film-forming material of the present invention having the alkali-soluble group is used as the resist film. An alkali developer is preferred because it can be dissolved and removed simultaneously with the uncured region. By performing development with the alkali developer, the resist cover film is dissolved and removed together with the portion of the resist film not irradiated with the exposure light, and a resist pattern is formed (developed).

Here, an example of a resist pattern forming method of the present invention will be described below with reference to the drawings.
As shown in FIG. 1, a resist forming material is applied onto a surface (substrate) 1 to be processed to form a resist film 2, and then a resist cover film forming material is applied to the surface of the resist film 2 and baked (processed). The resist cover film 3 is formed by heating and drying. And it exposes using the to-be-processed substrate 1 in which the resist film 2 and the resist cover film 3 were formed, and the immersion exposure apparatus 5 shown in FIG.
FIG. 2 is a schematic explanatory view showing an example of an immersion exposure apparatus. The immersion exposure apparatus 5 includes a stepper (sequential movement exposure apparatus) having a projection lens 6 and a wafer stage 7. The wafer stage 7 is provided so that the substrate 1 to be processed can be mounted, and a medium (liquid) 8 is filled between the projection lens 6 and the substrate 1 to be processed on the wafer stage 7. ing. The resolution of the stepper is expressed by the following formula (1). The shorter the wavelength of the light source, the larger the NA of the projection lens 6 (the brightness NA (numerical aperture) of the projection lens 6). The larger the size, the higher the resolution.
Resolution = k (process coefficient) × λ (wavelength of light from the light source) / NA (numerical aperture) (1)
In the formula (1), NA can be obtained by the following formula, NA = n × sin θ.
An enlarged view of the portion X in FIG. 2 is shown in FIG. As shown in FIG. 3, n represents the refractive index of the medium (liquid) 8 through which the exposure light passes, and θ represents the angle formed by the exposure light. In a normal exposure method, since the medium through which the exposure light passes is air, the refractive index n = 1, and the numerical aperture NA of the projection lens (reduction projection lens) 6 is theoretically less than 1.0 at the maximum. There is actually only about 0.9 (θ = 65 °). On the other hand, in the immersion exposure apparatus 5, by using a liquid having a refractive index n greater than 1 as the medium 8, n is enlarged. At the same incident light incident angle θ, the minimum resolution dimension is 1. / N, and with the same numerical aperture NA, θ can be reduced and the depth of focus can be increased n times. For example, when pure water is used as the medium 8, when the light source is ArF, n = 1.44, the NA can be increased up to 1.44 times, and a finer pattern can be formed. Can do.

The substrate 1 to be processed is placed on the wafer stage 7 of such an immersion exposure apparatus 5, and the resist film 2 is irradiated with exposure light (for example, ArF excimer laser light) in a pattern through the resist cover film 3. To expose. Next, when alkali development processing is performed, as shown in FIG. 4, the resist cover film 3 and the region of the resist film 2 that has not been irradiated with the ArF excimer laser light are dissolved and removed, and the substrate 1 is processed. A resist pattern 4 is formed (developed).
The above is an example of the resist pattern forming method of the present invention using a positive resist material corresponding to ArF excimer laser light, and the combination of exposure light and resist material is not limited to this. It can be selected as appropriate according to the conditions.

  According to the method for forming a resist pattern of the present invention, the resist film can be effectively protected from the liquid, and the exposure of the resist film can be performed with high precision by immersion exposure without impairing the function of the resist film. Fine resist patterns can be easily and efficiently formed. For example, mask patterns, reticle patterns, magnetic heads, LCDs (liquid crystal displays), PDPs (plasma display panels), SAW filters (surface acoustic wave filters), etc. It can be suitably applied to the production of electronic devices such as functional parts, optical parts used for connecting optical wiring, microparts such as microactuators, semiconductor devices, and the like, and suitable for the method for producing electronic devices of the present invention. Can be used.

(Electronic device manufacturing method)
The method for manufacturing an electronic device of the present invention includes at least a resist pattern forming step and a patterning step, and further includes other steps appropriately selected as necessary.

<Resist pattern formation process>
In the resist pattern forming step, after forming a resist film on a substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material of the present invention, and the resist cover film is interposed therebetween. In this step, the resist film is irradiated with exposure light by immersion exposure and developed to form a resist pattern. A resist pattern is formed on the substrate to be processed by the resist pattern forming step.
Details in the resist pattern forming step are the same as those of the resist pattern forming method of the present invention.
Examples of the surface to be processed include surface layers of various members in an electronic device such as a semiconductor device, and preferable examples include a substrate such as a silicon wafer or the surface thereof, various oxide films, and the like. The immersion exposure method is as described above. The resist pattern is as described above.

<Patterning process>
The patterning step is a step of patterning the substrate to be processed by etching using the resist pattern as a mask (using as a mask pattern or the like).
There is no restriction | limiting in particular as the said etching method, Although it can select suitably according to the objective from well-known methods, For example, dry etching is mentioned suitably. The etching conditions are not particularly limited and can be appropriately selected depending on the purpose.

  According to the method for manufacturing an electronic device of the present invention, high-definition exposure can be performed by immersion exposure without impairing the function of the resist film, and a fine and high-definition resist pattern can be easily and efficiently formed. Yes, to efficiently mass-produce high-performance electronic devices having fine wiring patterns formed using the resist pattern, for example, various semiconductor devices such as flash memory, DRAM, FRAM, etc. Can do.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Production Example 1)
-Preparation of resist cover film forming material (1)-
A silicon-containing polymer represented by the following structural formula (1) was dissolved in n-butyl alcohol to prepare a resist cover film forming material (1) for immersion exposure.

ただし、前記構造式（１）中、ｄは１であり、ｅは０．２である。

However, in said structural formula (1), d is 1 and e is 0.2.

(Production Example 2)
-Preparation of resist cover film forming material (2)-
A silicon-containing polymer represented by the following structural formula (2) was dissolved in isobutyl alcohol to prepare a resist cover film forming material (2) for immersion exposure.

ただし、前記構造式（２）中、ａは１．２であり、ｂは１であり、Ｃは０．４５である。

However, in said structural formula (2), a is 1.2, b is 1, and C is 0.45.

(Production Example 3)
-Preparation of resist cover film forming material (3)-
A silicon-containing polymer represented by the following structural formulas (1) and (2) is mixed at a weight ratio of 1: 4 and dissolved in n-butyl alcohol to form a resist cover film forming material (3 ) Was prepared.

ただし、前記構造式（１）中、ｄは１であり、ｅは０．２である。

ただし、前記構造式（２）中、ａは１．２であり、ｂは１であり、Ｃは０．４５である。

However, in said structural formula (1), d is 1 and e is 0.2.

However, in said structural formula (2), a is 1.2, b is 1, and C is 0.45.

Example 1
-Formation of resist pattern-
A resist material for ArF excimer laser light (“AX5910”; manufactured by Sumitomo Chemical Co., Ltd.) was applied on a silicon substrate to form a resist film having a thickness of 250 nm. Next, the resist cover film forming materials (1), (2), and (3) are spin-coated on the resist film under the conditions of 3500 rpm and 45 s by spin coating, respectively, and then heated on a 110 ° C. hot plate at 60 ° C. By baking for a second, a resist cover film having a thickness of 100 nm was formed, and three types of samples (samples (1) to (3)) were prepared.

Each of the resist films was exposed through the resist cover film using an immersion exposure apparatus. Note that water was used as a medium for immersion exposure, and ArF excimer laser light (wavelength 193 nm) was used as exposure light. Here, the ArF excimer laser light transmittances of the resist cover films in the samples (1) to (3) are 94% for the sample (1), 92% for the sample (2), and 94% for the sample (3), respectively. Met.
Next, the resist cover film and the resist film were subjected to alkali development with a 2.38 mass% TMAH aqueous solution to dissolve and remove the unexposed portions of the resist film and the resist cover film. As a result, in each sample, a 120 nm hole pattern (resist pattern) and a 140 nm line pattern (resist pattern) were obtained at an exposure amount of 39.0 mJ / cm ² .

(Reference Experiment 1)
In Example 1, a resist pattern was prepared for each of the samples (1) to (3) in which a resist cover film was formed in the same manner as in Example 1 except that the immersion exposure medium was changed from water to air. . As a result of ArF excimer laser exposure, a 130 nm hole pattern (resist pattern) and a 140 nm line pattern (resist pattern) were obtained with an exposure amount of 39.0 mJ / cm ² .

(Comparative Example 1)
In Example 1, except that the resist cover film was not formed, resist patterns were prepared for Samples (1) to (3) formed in the same manner as in Example 1, respectively. As a result of ArF excimer laser exposure, all samples had an exposure amount of 39.0 mJ / cm ² , 130 nm hole patterns were not opened, 140 nm line patterns were twisted, and high-definition patterns were not obtained. .

(Comparative Example 2)
Samples (1) to (3) formed in the same manner as in Example 1 except that the immersion exposure medium was changed from water to air in Example 1 and the resist cover film was not formed. A resist pattern was prepared for each. As a result of the ArF excimer laser exposure, a 130 nm hole pattern and a 140 nm line pattern were obtained with an exposure amount of 39.0 mJ / cm ² for each sample.

About each obtained resist pattern, hole resolution and line resolution were evaluated based on the following reference | standard. The results are shown in Table 1.
〔Evaluation criteria〕
○: A resist pattern with a prescribed hole size or line size could be resolved. ×: A resist pattern with a prescribed hole size or line size could not be resolved.

From Table 1, in Example 1, a resist cover film made of the resist cover film forming material of the present invention was formed on the resist film, and immersion exposure of the resist film was performed through the resist cover film. It was found that even when exposed using water as a medium, there was no change in resolution and sensitivity, and a fine and high-definition resist pattern was obtained without impairing the original resist performance. On the other hand, in Comparative Example 1, since the resist cover film was not formed, it was found that the resolution and sensitivity changed due to elution of the acid in the resist into water and a fine and high-definition resist pattern could not be obtained. It was.
Further, comparing the reference experiment 1 and the comparative example 2, the resist cover film of the present invention has a high exposure light transmittance, and even when formed on the resist film, the exposure sensitivity is not lowered, and the resolution is improved. It was found that an excellent, fine and high-definition resist pattern can be formed.

(Example 2)
As shown in FIG. 5, an interlayer insulating film 12 was formed on the silicon substrate 11, and as shown in FIG. 6, a titanium film 13 was formed on the interlayer insulating film 12 by sputtering. Next, as shown in FIG. 7, a resist pattern 14 is formed by a known photolithography technique using an immersion exposure method, and this is used as a mask, and the titanium film 13 is patterned by reactive ion etching to form openings. 15a was formed. Subsequently, the resist pattern 14 was removed by reactive ion etching, and an opening 15b was formed in the interlayer insulating film 12 using the titanium film 13 as a mask as shown in FIG.

  Next, the titanium film 13 is removed by wet processing, and as shown in FIG. 9, a TiN film 16 is formed on the interlayer insulating film 12 by a sputtering method. Subsequently, a Cu film 17 is formed on the TiN film 16 by an electrolytic plating method. The film was formed. Next, as shown in FIG. 10, CMP is performed to leave the barrier metal and Cu film (first metal film) only in the groove corresponding to the opening 15b (FIG. 8), and the first layer wiring 17a is formed. Formed.

  Next, as shown in FIG. 11, after the interlayer insulating film 18 is formed on the first layer wiring 17a, the first layer wiring 17a is formed as shown in FIG. Then, a Cu plug (second metal film) 19 and a TiN film 16a connected to an upper layer wiring to be formed later were formed.

By repeating the above steps, a multilayer wiring structure including a first layer wiring 17a, a second layer wiring 20, and a third layer wiring 21 was provided on the silicon substrate 11, as shown in FIG. A semiconductor device was manufactured. In FIG. 13, the illustration of the barrier metal layer formed under the wiring of each layer is omitted.
In Example 2, the resist pattern 14 is a resist pattern manufactured by performing immersion exposure using the resist cover film forming material of the present invention and manufacturing in the same manner as in Examples 1 to 3.

(Example 3)
-Flash memory and its manufacture-
Example 3 is an example of the manufacturing method of the electronic device of the present invention using the resist cover film forming material of the present invention. In Example 5, the following resist films 26, 27, 29 and 32 were formed by the same method as in Examples 1 and 2 using the resist cover film forming material of the present invention. .

  14 and 15 are top views (plan views) of a FLASH EPROM called a FLOTOX type or an ETOX type called a FLOTOX type or an ETOX type, and FIGS. FIG. 14 and FIG. 15 are schematic cross-sectional views for illustrating the memory cell portion (first element region) in the gate width direction of the portion where the MOS transistor having the floating gate electrode is formed. FIG. 6 is a schematic view of the cross section (direction A cross section) in the X direction, the central view is the memory cell portion of the same portion as the left view, and the gate length direction (Y in FIGS. 14 and 15) perpendicular to the X direction. Direction) cross section (B direction cross section) is a schematic diagram, and the right figure is a portion of the peripheral circuit portion (second element region) where the MOS transistor is formed FIG. 16 is a schematic view of a cross section (a cross section in the direction A in FIGS. 14 and 15).

First, as shown in FIG. 16, a field oxide film 23 made of a SiO ₂ film was selectively formed in an element isolation region on a p-type Si substrate 22. Thereafter, the first gate insulating film 24a in the MOS transistor in the memory cell portion (first element region) is formed by SiO ₂ film by thermal oxidation so that the thickness becomes 100 to 300 mm (10 to 30 nm). In the process, the second gate insulating film 24b in the MOS transistor in the peripheral circuit portion (second element region) was formed of a SiO ₂ film by thermal oxidation so as to have a thickness of 100 to 500 mm (10 to 50 nm). When the first gate insulating film 24a and the second gate insulating film 24b have the same thickness, an oxide film may be formed simultaneously in the same process.

Next, in order to form a MOS transistor having an n-type depletion type channel in the memory cell portion (left and center views in FIG. 16), the peripheral circuit portion (in FIG. (Right figure) was masked with a resist film 26. Then, phosphorus (P) or arsenic (As) with a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the floating gate electrode by an ion implantation method, A first threshold control layer 25a was formed. Note that the dose amount and the conductivity type of the impurity at this time can be appropriately selected depending on whether the depletion type or the accumulation type is used.

Next, in order to form a MOS transistor having an n-type depletion type channel in the peripheral circuit portion (the right diagram in FIG. 17), a memory cell portion (the left diagram in FIG. The resist film 27 was masked. Then, phosphorus (P) or arsenic (As) having a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the gate electrode by an ion implantation method. Two threshold control layers 25b were formed.

  Next, as the floating gate electrode of the MOS transistor in the memory cell portion (left and center diagrams in FIG. 18) and the gate electrode of the MOS transistor in the peripheral circuit portion (right diagram in FIG. 18), the thickness is 500-2. A first polysilicon film (first conductor film) 28 having a thickness of 1,000,000 (50 to 200 nm) was formed on the entire surface.

  After that, as shown in FIG. 19, the first polysilicon film 28 is patterned with a resist film 29 formed as a mask, so that the floating gate electrode 28a in the MOS transistor of the memory cell portion (the left diagram and the central diagram in FIG. 19) is formed. Formed. At this time, as shown in FIG. 19, patterning was performed so that the X direction had a final dimension width, and the Y direction was not patterned, and the region to be the S / D region layer was left covered with the resist film 29. .

Next, as shown in the left diagram and the central diagram of FIG. 20, after removing the resist film 29, the capacitor insulating film 30a made of the SiO ₂ film is formed so as to cover the floating gate electrode 28a. It formed by thermal oxidation so that it might become 200-500 mm (20-50 nm). At this time, the capacitor insulating film 30b made of the SiO ₂ film is also formed on the first polysilicon film 28 in the peripheral circuit portion (the right diagram in FIG. 20). Here, the capacitor insulating films 30a and 30b are formed of only the SiO ₂ film, but may be formed of a composite film in which two or _three SiO ₂ films and Si ₃ N ₄ films are laminated.

  Next, as shown in FIG. 20, the second polysilicon film (second conductor film) 31 to be the control gate electrode is coated with a thickness of 500 to 2 so as to cover the floating gate electrode 28a and the capacitor insulating film 30a. , And a thickness of 50 to 200 nm.

  Next, as shown in FIG. 21, the memory cell portion (the left and center views in FIG. 21) is masked with a resist film 32, and the second polysilicon film 31 in the peripheral circuit portion (the right view in FIG. 21). Then, the capacitor insulating film 30b was sequentially removed by etching, and the first polysilicon film 28 was exposed.

  Next, as shown in FIG. 22, the second polysilicon film 31, the capacitor insulating film 30a of the memory cell portion (the left diagram and the center diagram in FIG. 22), and the first polysilicon film 28a patterned only in the X direction. On the other hand, patterning in the Y direction is performed using the resist film 32 as a mask so as to have the final dimensions of the first gate portion 33a, and the control gate electrode 31a / capacitor insulating film 30c / floating gate having a width of about 1 μm in the Y direction. A stack of electrodes 28c is formed, and the final size of the second gate portion 33b is set with respect to the first polysilicon film 28 of the peripheral circuit portion (the right figure of FIG. 22) using the resist film 32 as a mask. Then, patterning was performed to form a gate electrode 28b having a width of about 1 μm.

Next, using the stack of the control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c of the memory cell portion (left and center views of FIG. 23) as a mask, the dose of 1 × is applied to the Si substrate 22 in the element formation region. 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² of phosphorus (P) or arsenic (As) is introduced by an ion implantation method to form n-type S / D region layers 35a and 35b, and the peripheral circuit portion (FIG. 23), using the gate electrode 28b of FIG. 23 as a mask, phosphorus (P) or arsenic (As) with a dose of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² as n-type impurities is applied to the Si substrate 22 in the element formation region. S / D region layers 36a and 36b were formed by ion implantation.

  Next, the first gate portion 33a of the memory cell portion (left and center views of FIG. 24) and the second gate portion 33b of the peripheral circuit portion (right portion of FIG. 24) are formed on the interlayer insulating film 37 made of PSG film. Was formed so as to have a thickness of about 5,000 mm (500 nm).

  Thereafter, contact holes 38a and 38b and contact holes 39a and 39b are formed in the interlayer insulating film 37 formed on the S / D region layers 35a and 35b and the S / D region layers 36a and 36b, and then the S / D electrode 40a. And 40b and S / D electrodes 41a and 41b were formed.

  As described above, as shown in FIG. 24, a FLASH EPROM was manufactured as a semiconductor device.

  In this FLASH EPROM, the second gate insulating film 24b of the peripheral circuit portion (right diagrams in FIGS. 16 to 24) is covered with the first polysilicon film 28 or the gate electrode 28b from the beginning to the end after the formation (FIG. 16 to FIG. 24), the second gate insulating film 24b maintains the thickness when it is first formed. Therefore, the thickness of the second gate insulating film 24b can be easily controlled, and the conductivity type impurity concentration for controlling the threshold voltage can be easily adjusted.

  In the above embodiment, the first gate portion 33a is formed by first patterning with a predetermined width in the gate width direction (X direction in FIGS. 14 and 15) and then in the gate length direction (in FIGS. 14 and 15). Patterning is performed in the Y direction) to obtain a final predetermined width, but conversely, after patterning with a predetermined width in the gate length direction (Y direction in FIGS. 14 and 15), the gate width direction (in FIGS. 14 and 15). The final predetermined width may be obtained by patterning in the X direction).

The manufacturing example of the FLASH EPROM shown in FIGS. 25 to 27 is the same as the above embodiment except that the steps shown in FIG. 26 in the above embodiment are changed as shown in FIGS. That is, as shown in FIG. 25, on the second polysilicon film 31 of the memory cell portion (left and center views in FIG. 25) and the first polysilicon film 28 of the peripheral circuit portion (right view of FIG. 25). Further, a refractory metal film (fourth conductor film) 42 made of a tungsten (W) film or a titanium (Ti) film is formed so as to have a thickness of about 2,000 mm (200 nm), and a polycide film is provided. Only differs from the above embodiment. The subsequent steps of FIG. 25, that is, the steps shown in FIGS. 26 to 27 were performed in the same manner as FIGS. The description of the same steps as in FIGS. 22 to 24 is omitted, and in FIGS. 25 to 27, the same components as those in FIGS. 22 to 24 are denoted by the same symbols.
As described above, as shown in FIG. 27, a FLASH EPROM was manufactured as a semiconductor device.

In this FLASH EPROM, since the refractory metal films (fourth conductor films) 42a and 42b are provided on the control gate electrode 31a and the gate electrode 28b, the electric resistance value can be further reduced.
Here, although the refractory metal films (fourth conductor film) 42a and 42b are used as the refractory metal film (fourth conductor film), a refractory metal silicide film such as a titanium silicide (TiSi) film is used. May be used.

The flash EPROM manufacturing example shown in FIGS. 28 to 30 is the same as that of the above-described embodiment in the second gate portion 33c of the peripheral circuit portion (second element region) (the right diagram in FIG. 30). 1 element region) (first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second, similarly to the first gate portion 33a in the left and middle diagrams in FIG. 28) The gate electrode is formed by short-circuiting the first polysilicon film 28b and the second polysilicon film 31b, as shown in FIG. 29 or FIG. 30, with the configuration of the polysilicon film 31b (second conductor film). Except for the differences, this embodiment is the same as the above embodiment.

Here, as shown in FIG. 29, the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is penetrated. The opening 52a is formed, for example, on a different location from the second gate portion 33c shown in FIG. 28, for example, on the insulating film 54, and a third conductor film such as a W film or a Ti film is formed in the opening 52a. By embedding the melting point metal film 53a, the first polysilicon film 28b and the second polysilicon film 31b are short-circuited. Further, as shown in FIG. 30, an opening 52b penetrating the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) is formed, and a lower layer is formed at the bottom of the opening 52b. After the first polysilicon film 28b is exposed, a third conductor film, for example, a refractory metal film 53b such as a W film or a Ti film is embedded in the opening 52b, whereby the first polysilicon film 28b and the first polysilicon film 28b are formed. 2 The polysilicon film 31b is short-circuited.

In this FLASH EPROM, since the second gate portion 33c of the peripheral circuit portion has the same structure as the first gate portion 33a of the memory cell portion, the peripheral circuit portion is simultaneously formed when the memory cell portion is formed. It can be formed, and the manufacturing process can be simplified and efficient.
Although the third conductor film 53a or 53b and the refractory metal film (fourth conductor film) 42 are separately formed here, they may be formed simultaneously as a common refractory metal film. Good.

Example 4
-Manufacture of magnetic heads-
Example 4 relates to the manufacture of a magnetic head as an application example of a resist pattern formed using the resist cover film forming material of the present invention. In Example 4, the following resist patterns 102 and 126 are formed by the same method as in Example 1 using the resist cover film forming material of the present invention.

31 to 34 are process diagrams for explaining the manufacture of the magnetic head.
First, as shown in FIG. 31, a resist film is formed on the interlayer insulating layer 100 so as to have a thickness of 6 μm, exposed and developed, and a resist having an opening pattern for forming a spiral thin film magnetic coil. A pattern 102 was formed.
Next, as shown in FIG. 32, Ti having a thickness of 0.01 μm on the interlayer insulating layer 100 on the resist pattern 102 and the portion where the resist pattern 102 is not formed, that is, on the exposed surface of the opening 104. A plating work surface 106 formed by laminating an adhesion film and a Cu adhesion film having a thickness of 0.05 μm was formed by vapor deposition.

Next, as shown in FIG. 33, the thickness of the portion of the interlayer insulating layer 100 where the resist pattern 102 is not formed, that is, the surface of the plating processing surface 106 formed on the exposed surface of the opening 104 is increased. A thin film conductor 108 made of a Cu plating film having a thickness of 3 μm was formed.
Next, as shown in FIG. 34, when the resist pattern 102 is dissolved and removed and lifted off from above the interlayer insulating layer 100, a thin film magnetic coil 110 having a spiral pattern of the thin film conductor 108 is formed.
A magnetic head was manufactured as described above.

  In the magnetic head obtained here, since the spiral pattern is finely formed by the resist pattern 102 formed by immersion exposure using the resist cover film forming material of the present invention, the thin film magnetic coil 110 is fine and It is fine and has excellent mass productivity.

35 to 40 are process diagrams for explaining the manufacture of another magnetic head.
As shown in FIG. 35, a gap layer 114 was formed on a ceramic nonmagnetic substrate 112 by sputtering. Although not shown, an insulating layer made of silicon oxide and a conductive work surface made of Ni—Fe permalloy are previously formed on the nonmagnetic substrate 112 by sputtering, and a lower portion made of Ni—Fe permalloy. A magnetic layer is formed. Then, a resin insulating film 116 was formed from a thermosetting resin in a predetermined region on the gap layer 114 excluding a portion that becomes a magnetic tip of the lower magnetic layer (not shown). Next, a resist material was applied onto the resin insulating film 116 to form a resist film 118.

  Next, as shown in FIG. 36, the resist film 118 was exposed and developed to form a spiral pattern. Then, as shown in FIG. 37, this spiral pattern resist film 118 was subjected to thermosetting treatment at several hundred degrees C. for about one hour to form a protruding first spiral pattern 120. Further, a conductive work surface 122 made of Cu was formed on the surface.

  Next, as shown in FIG. 38, a resist material is applied onto the conductive work surface 122 by spin coating to form a resist film 124, and then the resist film 124 is patterned on the first spiral pattern 120. Thus, a resist pattern 126 was formed.

Next, as shown in FIG. 39, a Cu conductor layer 128 was formed by plating on the exposed surface of the conductive workpiece surface 122, that is, on a portion where the resist pattern 126 was not formed. Thereafter, as shown in FIG. 40, the resist pattern 126 was dissolved and removed to lift off from the surface 122 to be processed, and a spiral thin film magnetic coil 130 formed of the Cu conductor layer 128 was formed.
Thus, a magnetic head having the magnetic layer 132 on the resin insulating film 116 and having the thin film magnetic coil 130 provided on the surface as shown in the plan view of FIG. 41 was manufactured.

  In the magnetic head obtained here, since the spiral pattern is finely formed by the resist pattern 126 formed by the immersion exposure method using the resist cover film forming material of the present invention, the thin film magnetic coil 130 is fine. It is fine and has excellent mass productivity.

ただし、前記一般式（１）中、Ｒ^１はアルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^２は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ａ、ｂ及びｃは比を表し、それぞれａ＞０、ｂ＞０、ｃ≧０である。

ただし、前記一般式（２）中、Ｒ^３及びＲ^４の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なくともいずれかを表し、Ｒ^５は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｄ、ｅ及びｆは比を表し、それぞれｄ＞０、ｅ≧０、ｆ≧０である。

ただし、前記一般式（３）中、Ｒ^６、Ｒ^７及びＲ^８の少なくともいずれかは、アルカリ可溶性基を有する一価の有機基及びトリオルガノシリル基の少なｓくともいずれかを表し、Ｒ^９は一価の有機基、トリオルガノシリル基、及び水酸基の少なくともいずれかを表す。ｇ、ｈ及びｉは比を表し、それぞれｇ＞０、ｈ≧０、ｉ≧０である。
（付記２） アルカリ可溶性基が、カルボン酸含有基である付記１に記載のレジストカバー膜形成材料。
（付記３） アルカリ可溶性基が、下記一般式（４）で表される付記１から２のいずれかに記載のレジストカバー膜形成材料。

ただし、前記一般式（４）中、ｍは、次式、０≦ｍ≦５、を充たす。
（付記４） 有機溶剤が、炭素数３以上の脂肪族アルカノールである付記１から３のいずれかに記載のレジストカバー膜形成材料。
（付記５） 液浸露光に用いられる露光光が、１９３ｎｍの波長を有するＡｒＦエキシマレーザ光、及び１５７ｎｍの波長を有するＦ_２エキシマレーザ光の少なくともいずれかである付記１から４のいずれかに記載のレジストカバー膜形成材料。
（付記６） レジストカバー膜の厚みが１００ｎｍのときの露光光透過率が３０％以上である付記５に記載のレジストカバー膜形成材料。
（付記７） レジストカバー膜の厚みが１００ｎｍのときの露光光透過率が８０％以上である付記５から６のいずれかに記載のレジストカバー膜形成材料。
（付記８） 被加工基板上にレジスト膜を形成した後、該レジスト膜上に付記１から７のいずれかに記載のレジストカバー膜形成材料を用いてレジストカバー膜を形成し、該レジストカバー膜を介して前記レジスト膜に対して液浸露光により露光光を照射し、現像することを特徴とするレジストパターンの形成方法。
（付記９） レジストカバー膜の厚みが、１０〜３００ｎｍである付記８に記載のレジストパターンの形成方法。
（付記１０） レジストカバー膜が、塗布により形成された付記８から９のいずれかに記載のレジストパターンの形成方法。
（付記１１） 現像が、アルカリ現像液を用いて行われる付記８から１０のいずれかに記載のレジストパターンの形成方法。
（付記１２） 液浸露光に用いられる液体の屈折率が１より大きい付記８から１１のいずれかに記載のレジストパターンの形成方法。
（付記１３） 液体が水である付記１２に記載のレジストパターンの形成方法。
（付記１４） 露光光が、１９３ｎｍの波長を有するＡｒＦエキシマレーザ光、及び１５７ｎｍの波長を有するＦ_２エキシマレーザ光の少なくともいずれかである付記８から１３のいずれかに記載のレジストパターンの形成方法。
（付記１５） 被加工基板上にレジスト膜を形成した後、該レジスト膜上に付記１から７のいずれかに記載のレジストカバー膜形成材料を用いてレジストカバー膜を形成し、該レジストカバー膜を介して前記レジスト膜に対して液浸露光により露光光を照射し、現像することによりレジストパターンを形成するレジストパターン形成工程と、該レジストパターンをマスクとしてエッチングにより前記被加工基板をパターニングするパターニング工程とを含むことを特徴とする電子デバイスの製造方法。
（付記１６） レジストカバー膜が、塗布により形成された付記１５に記載の電子デバイスの製造方法。
（付記１７） 付記１５から１６のいずれかに記載の電子デバイスの製造方法により製造されたことを特徴とする電子デバイス。 The preferred embodiments of the present invention are as follows.
(Appendix 1) Used for forming a resist cover film that covers the resist film when immersion exposure is performed on the resist film, and has at least an alkali-soluble group and is represented by the following general formulas (1) to (3) A resist cover film-forming material comprising at least one selected from the group consisting of silicon-containing polymers represented by the formula (1) and an organic solvent capable of dissolving the silicon-containing polymer.

In the general formula (1), R ¹ represents at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, R ² represents a monovalent organic group, a triorganosilyl group, and It represents at least one of hydroxyl groups. a, b, and c represent ratios, where a> 0, b> 0, and c ≧ 0, respectively.

However, in the general formula (2), at least one of R ³ and R ^{4 represents} at least one of a monovalent organic group and a triorganosilyl group having an alkali-soluble group, and R ⁵ is a monovalent organic group. Represents at least one of a group, a triorganosilyl group, and a hydroxyl group. d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively.

However, in the general formula (3), at least one of R ⁶ , R ⁷ and R ^{8 represents} at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, and R ⁹ represents at least one of a monovalent organic group, a triorganosilyl group, and a hydroxyl group. g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively.
(Supplementary note 2) The resist cover film forming material according to supplementary note 1, wherein the alkali-soluble group is a carboxylic acid-containing group.
(Supplementary note 3) The resist cover film-forming material according to any one of supplementary notes 1 to 2, wherein the alkali-soluble group is represented by the following general formula (4).

However, in the general formula (4), m satisfies the following formula, 0 ≦ m ≦ 5.
(Supplementary note 4) The resist cover film forming material according to any one of supplementary notes 1 to 3, wherein the organic solvent is an aliphatic alkanol having 3 or more carbon atoms.
(Supplementary Note 5) Any one of Supplementary Notes 1 to 4, wherein the exposure light used for immersion exposure is at least one of ArF excimer laser light having a wavelength of 193 nm and F ₂ excimer laser light having a wavelength of 157 nm. Resist cover film forming material.
(Additional remark 6) The resist cover film forming material of Additional remark 5 whose exposure light transmittance is 30% or more when the thickness of a resist cover film is 100 nm.
(Supplementary note 7) The resist cover film-forming material according to any one of supplementary notes 5 to 6, wherein the exposure light transmittance is 80% or more when the thickness of the resist cover film is 100 nm.
(Additional remark 8) After forming a resist film on a to-be-processed substrate, a resist cover film is formed on the resist film using the resist cover film formation material in any one of additional remarks 1-7, and this resist cover film The resist pattern is formed by irradiating the resist film with immersion light through immersion exposure and developing.
(Additional remark 9) The resist pattern formation method of Additional remark 8 whose thickness of a resist cover film | membrane is 10-300 nm.
(Supplementary note 10) The method for forming a resist pattern according to any one of supplementary notes 8 to 9, wherein the resist cover film is formed by coating.
(Additional remark 11) The formation method of the resist pattern in any one of additional remark 8 to 10 with which development is performed using an alkali developing solution.
(Supplementary note 12) The method for forming a resist pattern according to any one of Supplementary notes 8 to 11, wherein the refractive index of the liquid used for immersion exposure is greater than 1.
(Additional remark 13) The formation method of the resist pattern of Additional remark 12 whose liquid is water.
(Supplementary Note 14) The method for forming a resist pattern according to any one of Supplementary Notes 8 to 13, wherein the exposure light is at least one of ArF excimer laser light having a wavelength of 193 nm and F ₂ excimer laser light having a wavelength of 157 nm. .
(Additional remark 15) After forming a resist film on a to-be-processed substrate, a resist cover film is formed on this resist film using the resist cover film forming material in any one of Additional remarks 1-7, and this resist cover film A resist pattern forming step of forming a resist pattern by irradiating the resist film with immersion light by immersion exposure and developing, and patterning the substrate to be processed by etching using the resist pattern as a mask A method for manufacturing an electronic device.
(Additional remark 16) The manufacturing method of the electronic device of Additional remark 15 with which the resist cover film | membrane was formed by application | coating.
(Appendix 17) An electronic device manufactured by the method for manufacturing an electronic device according to any one of appendices 15 to 16.

Since the resist cover film forming material of the present invention has high transmittance for ArF excimer laser light and F ₂ excimer laser light, the refractive index n is 1 (the refractive index of air) between the projection lens of the exposure apparatus and the wafer. In an immersion exposure technique that realizes an improvement in resolution by filling a larger medium (liquid), it can be suitably used as a resist cover film for immersion exposure that protects the resist film from the liquid.
The resist pattern forming method of the present invention includes, for example, a mask pattern, a reticle pattern, a magnetic head, an LCD (liquid crystal display), a PDP (plasma display panel), a SAW filter (surface acoustic wave filter), and other functional parts, The present invention can be suitably applied to the production of electronic devices such as optical components, microactuators such as microactuators and semiconductor devices used for connection, and can be suitably used in the method for producing electronic devices of the present invention.
The method for manufacturing an electronic device of the present invention can be suitably used for manufacturing the electronic device of the present invention. The electronic device of the present invention can be suitably used in the fields of various semiconductor devices including flash memory, DRAM, FRAM, and the like.

FIG. 1 is a schematic view for explaining an example of a resist pattern forming method of the present invention, and shows a state in which a resist cover film is formed. FIG. 2 is a schematic diagram for explaining an example of a resist pattern forming method of the present invention, and represents an example of an immersion exposure apparatus. FIG. 3 is a partially enlarged view of the immersion exposure apparatus shown in FIG. FIG. 4 is a schematic diagram for explaining an example of a resist pattern forming method of the present invention, and shows a state in which development is performed after immersion exposure using a resist cover film. FIG. 5 is a schematic view for explaining an example of a method for manufacturing an electronic device according to the present invention, and shows a state in which an interlayer insulating film is formed on a silicon substrate. FIG. 6 is a schematic view for explaining an example of the method for manufacturing an electronic device of the present invention, and shows a state in which a titanium film is formed on the interlayer insulating film shown in FIG. FIG. 7 is a schematic diagram for explaining an example of a method for manufacturing an electronic device of the present invention, and shows a state in which a resist film is formed on a titanium film and a hole pattern is formed on the titanium layer. FIG. 8 is a schematic view for explaining an example of a method for manufacturing an electronic device according to the present invention, and shows a state in which a hole pattern is also formed in an interlayer insulating film. FIG. 9 is a schematic diagram for explaining an example of a method for manufacturing an electronic device of the present invention, and shows a state in which a Cu film is formed on an interlayer insulating film in which a hole pattern is formed. FIG. 10 is a schematic diagram for explaining an example of a method for manufacturing an electronic device according to the present invention, and shows a state in which Cu deposited on an interlayer insulating film other than on the hole pattern is removed. FIG. 11 is a schematic diagram for explaining an example of a method for manufacturing an electronic device according to the present invention, and shows a state in which an interlayer insulating film is formed on a Cu plug and an interlayer insulating film formed in a hole pattern. FIG. 12 is a schematic diagram for explaining an example of a method for manufacturing an electronic device of the present invention, and shows a state in which a hole pattern is formed in an interlayer insulating film as a surface layer and a Cu plug is formed. FIG. 13 is a schematic view for explaining an example of a method for manufacturing an electronic device according to the present invention, and shows a state in which a wiring having a three-layer structure is formed. FIG. 14 is a plan view showing a first example of a FLASH EPROM manufactured by the electronic device manufacturing method of the present invention. FIG. 15 is a plan view showing a first example of a FLASH EPROM manufactured by the electronic device manufacturing method of the present invention. FIG. 16 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention. FIG. 17 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 18 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 19 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 20 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 21 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 22 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 23 is a schematic explanatory view of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 24 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing an electronic device of the present invention, and represents the next step of FIG. FIG. 25 is a schematic explanatory view of a second example of the manufacture of FLASH EPROM by the electronic device manufacturing method of the present invention. FIG. 26 is a schematic explanatory view of a second example of the manufacture of the FLASH EPROM by the electronic device manufacturing method of the present invention, and represents the next step of FIG. FIG. 27 is a schematic explanatory view of a second example of the manufacture of FLASH EPROM by the electronic device manufacturing method of the present invention, and represents the next step of FIG. FIG. 28 is a schematic explanatory diagram of a third example of the manufacture of FLASH EPROM by the electronic device manufacturing method of the present invention. FIG. 29 is a schematic explanatory view of a third example of the manufacture of the FLASH EPROM by the electronic device manufacturing method of the present invention, and represents the next step of FIG. FIG. 30 is a schematic explanatory view of a third example of the manufacture of the FLASH EPROM by the electronic device manufacturing method of the present invention, and represents the next step of FIG. FIG. 31 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head. FIG. 32 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 33 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 34 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 35 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 36 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 37 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 38 is a schematic cross-sectional explanatory view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 39 is a schematic sectional view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 40 is a schematic cross-sectional view of an example in which a resist pattern formed by immersion exposure using the resist cover film forming material of the present invention is applied to the manufacture of a magnetic head, and represents the next step of FIG. FIG. 41 is a plan view showing an example of a magnetic head manufactured through the steps of FIGS.

Explanation of symbols

1 Surface to be processed (substrate)
2 resist film 3 resist cover film (resist cover film forming material of the present invention)
4 resist pattern 5 immersion exposure apparatus 6 projection lens 7 wafer stage 8 medium (liquid)
DESCRIPTION OF SYMBOLS 11 Silicon substrate 12 Interlayer insulation film 13 Titanium film 14 Resist pattern 15a Opening part 15b Opening part 16 TiN film 16a TiN film 17 Cu film 17a Wiring 18 Interlayer insulating film 19 Cu plug 20 Wiring 21 Wiring 22 Si substrate (semiconductor substrate)
23 field oxide film 24a first gate insulating film 24b second gate insulating film 25a first threshold control layer 25b second threshold control layer 26 resist film 27 resist film 28 first polysilicon layer (first conductor film)
28a Floating gate electrode 28b Gate electrode (first polysilicon film)
28c Floating gate electrode 29 Resist film 30a Capacitor insulating film 30b Capacitor insulating film 30c Capacitor insulating film 30d SiO ₂ film 31 Second polysilicon layer (second conductor film)
31a Control gate electrode 31b Second polysilicon film 32 Resist film 33a First gate part 33b Second gate part 33c Second gate part 35a S / D (source / drain) region layer 35b S / D (source / drain) region layer 36a S / D (source / drain) region layer 36b S / D (source / drain) region layer 37 Interlayer insulating film 38a Contact hole 38b Contact hole 39a Contact hole 39b Contact hole 40a S / D (source / drain) electrode 40b S / D (source / drain) electrode 41a S / D (source / drain) electrode 41b S / D (source / drain) electrode 42 refractory metal film (fourth conductor film)
42a refractory metal film (fourth conductor film)
42b refractory metal film (fourth conductor film)
44a First gate portion 44b Second gate portion 45a S / D (source / drain) region layer 45b S / D (source / drain) region layer 46a S / D (source / drain) region layer 46b S / D (source / drain) region layer Drain) region layer 47 Interlayer insulating film 48a Contact hole 48b Contact hole 49a Contact hole 49b Contact hole 50a S / D (source / drain) electrode 50b S / D (source / drain) electrode 51a S / D (source / drain) electrode 51b S / D (Source / Drain) Electrode 52a Opening 52b Opening 53a Refractory Metal Film (Third Conductor Film)
53b refractory metal film (third conductor film)
54 Insulating film 100 Interlayer insulating layer 102 Resist pattern 104 Opening 106 Surface to be plated 108 Thin film conductor (Cu plating film)
DESCRIPTION OF SYMBOLS 110 Thin film magnetic coil 112 Nonmagnetic board | substrate 114 Gap layer 116 Resin insulating layer 118 Resist film 118a Resist pattern 120 1st spiral pattern 122 Conductive processed surface 124 Resist film 126 Resist pattern 128 Cu conductor film 130 Thin film magnetic coil 132 Magnetic layer

Claims (4)

Used to form a resist cover film that covers the resist film when performing immersion exposure on the resist film, and has at least an alkali-soluble group and is represented by the following general formulas (1) to (3) A resist cover film-forming material comprising at least one selected from silicon-containing polymers and an organic solvent capable of dissolving the silicon-containing polymer.

In the general formula (1), R ¹ represents at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, R ² represents a monovalent organic group, a triorganosilyl group, and Represents at least one of hydrogen atoms . a, b, and c represent ratios, where a> 0, b> 0, and c ≧ 0, respectively .

However, in the general formula (2), at least one of R ³ and R ^{4 represents} at least one of a monovalent organic group and a triorganosilyl group having an alkali-soluble group, and R ⁵ is a monovalent organic group. Represents at least one of a group, a triorganosilyl group, and a hydrogen atom . d, e, and f represent ratios, and d> 0, e ≧ 0, and f ≧ 0, respectively. However, the case of d = 1 and e = f = 0 is excluded.

However, in the general formula (3), at least one of R ⁶ , R ⁷ and R ^{8 represents} at least one of a monovalent organic group having an alkali-soluble group and a triorganosilyl group, and R ⁹ is one. It represents at least one of a valent organic group, a triorganosilyl group, and a hydrogen atom . g, h, and i represent ratios, and g> 0, h ≧ 0, and i ≧ 0, respectively. However, the case where g = 1 and h = i = 0 is excluded.   The resist cover film forming material according to claim 1, wherein the alkali-soluble group is a carboxylic acid-containing group.   After forming a resist film on the substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material according to claim 1, and the resist cover film is interposed therebetween. A resist pattern forming method, wherein the resist film is irradiated with exposure light by immersion exposure and developed. After forming a resist film on the substrate to be processed, a resist cover film is formed on the resist film using the resist cover film forming material according to claim 1, and the resist cover film is interposed therebetween. A resist pattern forming step of forming a resist pattern by irradiating the resist film with exposure light by immersion exposure and developing, and a patterning step of patterning the substrate to be processed by etching using the resist pattern as a mask An electronic device manufacturing method comprising:

Images