JP4644014B2 - Resist cover film forming material, resist pattern forming method, semiconductor 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. The present invention relates to 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, a method for forming a resist pattern using the material, a semiconductor device, and a method for manufacturing the same.

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 processing surface on which a thin film is formed with a resist film, performing selective exposure, and developing to form a resist pattern, and then using the resist pattern as a mask for dry etching 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 enormous cost is required to improve the exposure apparatus aimed at realizing a shorter wavelength of the exposure light source. In recent years, ArF (argon fluoride) excimer laser light (wavelength 193 nm) has been put into practical use as exposure light instead of KrF (krypton fluoride) excimer laser light (wavelength 248 nm) that has been used conventionally. In order to cope with further miniaturization in the future, F ₂ excimer laser light (wavelength 157 nm) and EUV (ultra-ultraviolet light: wavelength 13 nm) having a wavelength shorter than that of the ArF excimer laser light have been studied. The equipment cost including development costs is very high, and it is expected that it will take a lot of time for practical use. 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. In addition, 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. Furthermore, resist components dissolved in water also cause the projection lens to become dirty. 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 wavelength shorter than the ArF excimer laser light (157 nm) are difficult to transmit normal organic matter, and due to the presence of the resist cover film, Since exposure failure occurs, the range of selection of usable materials is extremely narrow, and there is a problem that removal after exposure is not easy even if a material usable for the resist cover film can be selected.

Therefore, the resist film can be formed without being dissolved, the resist film can be effectively protected from the liquid having a high refractive index, and the resist characteristic deterioration and the occurrence of lens contamination can be suppressed. The ArF excimer A material that can be used for a resist cover film for immersion exposure that can transmit laser light and the F ₂ excimer laser light, and can be easily removed, and a related technology using the material have not been developed. However, the 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 that can impart hydrophobicity to a surface to be exposed.
Further, the present invention can effectively protect the resist film from the liquid and perform high-definition exposure by immersion exposure without impairing the function of the resist film and suppressing the occurrence of lens contamination. An object of the present invention is to provide a resist pattern forming method capable of easily and efficiently forming a fine and high-definition resist pattern.
Further, the present invention can form a fine and high-definition resist pattern by immersion exposure while suppressing the occurrence of the lens contamination without impairing the function of the resist film, and formed using the resist pattern. A method for manufacturing a semiconductor device capable of efficiently mass-producing a high-performance semiconductor device having a fine wiring pattern, and a high-performance semiconductor device having a fine wiring pattern manufactured by the semiconductor device manufacturing method The purpose is 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, if a material capable of reducing the surface energy of the exposure target surface by 20 mN / m or more before and after the formation of the resist cover film is used as the resist cover film forming material, the resist film is not dissolved. A resist cover film can be formed, and the hydrophobicity of the surface to be exposed (resist film surface) can be improved, and the resist film is effectively made from a high refractive index liquid filled between the projection lens and the wafer. It was found that it was possible to protect and suppress the deterioration of resist characteristics and the occurrence of lens contamination. Further, the present inventors have found that the resist cover film forming material can transmit ArF excimer laser light and F ₂ excimer laser light, and can be easily removed, thereby completing the present invention.

This invention is based on the said knowledge of this inventor, and as a means for solving the said subject, it is as the description of the below-mentioned supplementary note. 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 performing immersion exposure on the resist film, and the surface to be exposed before and after the formation of the resist cover film. The surface energy is reduced by 20 mN / m or more. For this reason, in the resist cover film formed using the resist cover film forming material, the surface energy of the exposure target surface (resist film surface) is reduced, and the hydrophobicity of the exposure target surface is improved, and the exposure target It is possible to effectively protect the surface from the high refractive index liquid filled between the projection lens and the wafer, and to suppress resist characteristic deterioration and occurrence of the lens contamination. The resist cover film forming material can transmit ArF excimer laser light and F ₂ excimer laser light, and can be easily removed.

In the method for forming a resist pattern of the present invention, after a film having at least a resist film is formed on the surface to be processed, the surface energy of the surface to be exposed is reduced by 20 mN / m or more on the film before and after the formation of the resist cover film. A resist cover film is formed using the resist cover film forming material to be developed, and the resist film is irradiated with exposure light by liquid immersion exposure through the resist cover film and developed.
In the resist pattern forming method, after a film having at least a resist film is formed on the surface to be processed, the resist cover film is formed on the film using the resist cover film forming material. Since the resist cover film is formed of the resist cover film forming material that reduces the surface energy of the exposure target surface (resist surface) by 20 mN / m or more before and after formation, the hydrophobicity of the exposure target surface is improved. The The resist film is exposed to the exposure light by the immersion exposure through the resist cover film. During the exposure, the resist cover film improves the hydrophobicity of the surface to be exposed, so that the resist film is effectively protected from the high refractive index liquid filled between the projection lens and the wafer. Further, resist characteristic deterioration and occurrence of the lens contamination are suppressed. When the resist cover film is formed by causing a resist cover film forming material to interact with the surface of the film having at least the resist film, the film having at least the resist film is not dissolved. Further, since the resist cover film forming material can transmit ArF excimer laser light or F ₂ excimer laser light, the exposure is performed with high definition. The resist cover film can be easily removed using a specific solvent. It is then developed. As a result, a resist pattern is easily and efficiently formed. The resist pattern obtained in this way is fine and fine because exposure is performed with high definition without impairing the function of the resist film.

The semiconductor device manufacturing method of the present invention includes a resist pattern forming step of forming a resist pattern on the processing surface using the resist pattern forming method of the present invention, and the processing surface by etching using the resist pattern as a mask. And a patterning process for patterning.
In the semiconductor device manufacturing method, first, in the resist pattern forming step, a pattern such as a wiring pattern is formed on the surface to be processed using the resist pattern forming method of the present invention. In the resist pattern formation step, the resist pattern forming method of the present invention performs immersion exposure with high definition without impairing the function of the resist film, so that a fine and high definition resist pattern is formed. Next, in the patterning step, etching is performed using the resist pattern formed in the resist pattern forming step. As a result, the surface to be processed is finely and finely patterned with high dimensional accuracy, and a high-quality and high-performance semiconductor device having an extremely fine and high-definition and excellent dimensional accuracy such as a wiring pattern is efficient. Well manufactured.
A semiconductor device of the present invention is manufactured by the method for manufacturing a semiconductor device of the present invention. The semiconductor device has a pattern such as a wiring pattern that is extremely fine and high-definition and excellent in 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. In the above, the resist cover film for immersion exposure that protects the resist film from the liquid can be suitably used, and a resist cover film forming material capable of imparting hydrophobicity to the surface to be exposed can be provided.
Further, according to the present invention, the resist film is effectively protected from the liquid, and the high-definition exposure is performed by immersion exposure without impairing the function of the resist film and suppressing the occurrence of lens contamination. It is possible to provide a method for forming a resist pattern that can easily and efficiently form a fine and high-definition resist pattern.
Further, according to the present invention, it is possible to form a fine and high-definition resist pattern by immersion exposure while suppressing the occurrence of the lens stain without impairing the function of the resist film, and using the resist pattern. A method for manufacturing a semiconductor device capable of efficiently mass-producing a high-performance semiconductor device having a fine wiring pattern, and a high-performance semiconductor device having a fine wiring pattern manufactured by the method for manufacturing the semiconductor device. Can be provided.

(Resist cover film forming material)
The resist cover film forming material of the present invention is used to form a resist cover film that covers the resist film when performing immersion exposure on the resist film, and the surface to be exposed before and after the formation of the resist cover film. Is reduced by 20 mN / m or more.

The resist cover film forming material is not particularly limited as long as it reduces the surface energy of the exposure target surface by 20 mN / m or more, and can be appropriately selected according to the purpose. It is preferable to reduce the energy by 25 mN / m or more.
When the surface energy of the exposure target surface is reduced by 20 mN / m or more before and after the formation of the resist cover film, the hydrophobicity of the exposure target surface is improved, and the liquid immersion without impairing the function of the resist film. The exposure can be performed with high definition.

There is no restriction | limiting in particular as surface energy of the said exposure object surface after the said resist cover film formation, Although it can select suitably according to the objective, It is so preferable that it is low, for example, 30 mN / m or less is preferable, 20 mN / m The following is more preferable.
When the surface energy of the surface to be exposed after the resist cover film is formed exceeds 30 mN / m, the surface of the surface to be exposed is inferior in hydrophobicity, the resist component may be dissolved, and the function of the resist film may be deteriorated. In addition, the dissolved resist component may contaminate the lens of the immersion exposure apparatus, resulting in a decrease in resolution due to poor exposure.
The surface to be exposed means the outermost surface of the film to be exposed. When the film to be exposed is formed only from the resist film before the formation of the resist cover film, the resist film In the case of a laminated film having another film such as an antireflection film on the resist film, the surface of the film located on the outermost part of the laminated film. On the other hand, after the resist cover film is formed, the surface of the resist cover film becomes the surface to be exposed.

  As a method for measuring the surface energy of the surface to be exposed, for example, a contact angle meter (“CA-QI”; manufactured by Kyowa Interface Science) is used to measure the contact angle of the surface to be exposed to pure water, for example. Can be sought.

The component of the resist cover film forming material is not particularly limited and may be appropriately selected depending on the intended purpose. However, it preferably includes at least an amphiphilic substance and, if necessary, other components appropriately selected. Ingredients may be included.
When the amphiphilic substance is contained, in the resist pattern forming method of the present invention described later, a resist cover film can be easily formed by the interaction between the surface to be exposed and the hydrophilic portion in the amphiphilic substance. The hydrophobic surface of the amphiphilic substance can impart hydrophobicity to the surface to be exposed.

-Amphiphile-
The amphiphilic substance is not particularly limited as long as it has both a hydrophilic part and a hydrophobic part in one molecule, and can be appropriately selected according to the purpose, but preferably contains at least fluorine. In general, it is advantageous in that the effect of reducing the surface energy of the surface to be exposed can be increased by substituting hydrogen of hydrocarbons with fluorine.
The amphiphile preferably has a polar group. In this case, the amphiphile easily interacts with the surface to be exposed by the polar group.
There is no restriction | limiting in particular as said polar group, According to the objective, it can select suitably, For example, OH group, CN group, a fluorine atom, a chlorine atom etc. are mentioned. Among these, an OH group is preferable because it can easily interact with a hydrophilic film.

The amphiphilic substance is a linear compound, and preferably has the polar group at least at one end of the linear chain. The presence of the polar group at one or both ends of the straight chain is advantageous in that the interaction is easily performed.
As the bonding position of the polar group in the linear compound, it may be positioned bonded to carbon atoms at both ends of the linear chain, or may be positioned bonded to carbon atoms at one terminal of the linear chain. You may do it. Depending on the length of the straight chain, for example, in the former case, the polar groups located at both ends interact with the hydrophilic film, and the linear compound is formed in an arc shape on the surface of the film. In the latter case, the polar group located at one end interacts with the hydrophilic membrane, and the linear compound exists linearly in the direction facing the surface of the membrane.

As a specific example of the amphiphilic substance, even when ArF excimer laser light having a wavelength of 193 nm or F ₂ excimer laser light having a wavelength of 157 nm is low in absorption, when formed on a resist film and exposed, For example, a substance represented by the following general formula (1) is preferably used because a resist pattern can be formed by transmitting these laser beams. These may be used individually by 1 type and may use 2 or more types together.

In the general formula (1), R may be the same as or different from each other, and is a group represented by any one of the following structural formulas (1) to (3). m represents an integer of 1 or more, and is preferably 5 or more in that a hydrophobic surface capable of effectively protecting the resist film from the liquid used for immersion exposure is obtained. 10-50 are more preferable at the point which can obtain a medicinal property.
The average molecular weight of the amphiphilic substance represented by the general formula (1) is preferably 2,000 to 6,000, for example, from the viewpoint of excellent adsorptivity to the hydrophilic film.

However, in the structural formula (2), n represents an integer of 1 or more, and 1 is preferable in order to increase the fluorine content, but the byproduct n is 2 to 10. It may be.

-Other ingredients-
The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, and include various known additives.
The content of the other components in the resist cover film forming material can be appropriately determined according to the type and content of the amphiphile and the like.

-Use-
The resist cover film-forming material of the present invention is preferably used by coating on a film having at least a resist film, and the coating method is not particularly limited and can be appropriately selected according to the purpose. For example, there is a method in which a coating solution obtained by dissolving the resist cover film forming material in a solvent is applied by spin coating.
There is no restriction | limiting in particular as content in the said coating liquid of the said resist cover film forming material, Although it can select suitably according to the objective, 0.01-1.0 mass% is preferable, 0.05-0 More preferably, it is 2% by mass.
When the content is less than 0.01% by mass, film-formability may be deteriorated such as generation of pinholes. When the content is more than 1.0% by mass, a resist by the amphiphilic substance adsorbed. The cover film increases in thickness, making it difficult for exposure light to pass therethrough and reducing the resolution.

When the resist cover film forming material is applied onto a film having at least a resist film, a resist cover film is formed on the film. At this time, since the resist cover film forming material lowers the surface energy of the exposure target surface by 20 mN / m or more, the hydrophobicity of the exposure target surface is improved. In addition, when the resist cover film forming material contains the specific amphiphile, the resist resist has low 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. A resist pattern can also be formed when it is applied on the film and exposed. Further, when the amphiphilic substance contains at least fluorine, it can be easily removed using a solvent containing fluorine.

The exposure light transmittance of the resist cover film is, for example, preferably 95% or more, and more preferably 99% or more when the thickness is 10 nm. If the exposure light transmittance is less than 95%, 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 light, F ₂ excimer laser beam, and the like. Among these, it is preferable to have a short wavelength of 260 nm or less from the viewpoint that a high-definition resist pattern can be formed. For example, ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm), and the like are preferable.

-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 (the resist film forming material) may contain an acid generator. In this case, during the immersion exposure, the acid content from the generator dissolves from the resist film and deteriorates the characteristics of the resist film. However, the resist cover film made of the resist cover film-forming material of the present invention is used. By forming it, the characteristic deterioration of the resist film can be effectively suppressed.
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 0.1 to 2 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. It can be used, and can be particularly suitably used for the resist cover film in the following resist pattern forming method and semiconductor device manufacturing method of the present invention.

(Method for forming resist pattern)
In the method for forming a resist pattern of the present invention, after forming a film having at least a resist film on the surface to be processed, a resist cover film is formed on the film using a resist cover film forming material, 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 film having at least a resist film on the surface to be processed.
The film having at least the resist film may have another film as long as it has at least the resist film, and the other film is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include an antireflection film.
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 antireflection film is a film formed so as to cover the surface of the resist film, and has a function of preventing halation from occurring due to a standing wave generated by reflecting the exposure light from the surface to be processed.
There is no restriction | limiting in particular as a material of the said antireflection film, According to the objective, it can select suitably, For example, acrylic acid etc. are mentioned.
In addition, there is no restriction | limiting in particular as thickness of the said antireflection film, Although it can select suitably according to the objective, For example, 40-200 nm is preferable.
If the thickness of the antireflection film is less than 40 nm, film defects such as pinholes may occur frequently. If the thickness exceeds 200 nm, the exposure light transmittance may be reduced.

The resist film and the antireflection 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 a semiconductor device or the like, the surface to be processed (base material) ) Includes the surface of a semiconductor substrate, 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 used to form a resist cover film that covers the resist film when immersion exposure is performed on the resist film on the film having at least the resist film. A step of forming a resist cover film using a resist cover film forming material that reduces the surface energy of the exposure target surface by 20 mN / m or more before and after the formation of the cover film, and using the resist cover film forming material of the present invention, It is preferable to form a resist cover film.
When the resist cover film forming material of the present invention is used as the resist cover film forming material, the surface energy of the exposure target surface can be reduced, and the hydrophobicity of the exposure target surface can be improved. The surface of the exposure object can be effectively protected from the liquid for immersion exposure, the resist characteristic deterioration and the occurrence of the lens contamination can be suppressed, and the immersion exposure can be performed with high definition.

In the resist cover film forming step, the surface energy of the exposure target surface after forming the resist cover film is preferably 30 mN / m or less, and more preferably 20 mN / m or less.
When the surface energy of the surface to be exposed after the resist cover film is formed exceeds 30 mN / m, the surface of the surface to be exposed is inferior in hydrophobicity, and the resist component dissolves and the function of the resist film is deteriorated. In addition, the dissolved resist component may contaminate the lens of the immersion exposure apparatus, resulting in a decrease in resolution due to poor exposure.
The details of the exposure target surface are as described above in the resist cover film forming material.

The resist cover film is preferably formed by allowing a resist cover film forming material to interact with the surface of the film having at least the resist film.
Examples of the resist cover film forming material include those described above in the resist cover film forming material of the present invention, and it is particularly preferable that the resist cover film forming material contains at least the amphiphilic substance.

The mode of the interaction is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably at least one of chemical adsorption and physical adsorption.
There is no restriction | limiting in particular as said chemical adsorption, According to the objective, it can select suitably, For example, a covalent bond, a hydrogen bond, a coordination bond, an ionic bond etc. are mentioned.
There is no restriction | limiting in particular as said physical adsorption, According to the objective, it can select suitably, For example, intermolecular force (Van der Waals force), adhesion, etc. are mentioned, for example.
When the resist cover film-forming material contains the amphiphilic substance, the hydrophilic portion in the amphiphilic substance interacts with the surface of the film having at least the resist film, and the parents are formed on the surface of the film. The medium is regularly arranged. As a result, the hydrophobic portion in the amphiphile is disposed on the outermost surface of the film, and constitutes the exposure target surface. For this reason, the hydrophobicity of the surface to be exposed is improved, and the characteristic deterioration of the resist film is suppressed.
In particular, when the amphiphilic substance is used to form the amphiphilic monomolecular film by the interaction, a defect-free ultrathin film (for example, LB film) resist cover film can be formed.

The resist cover film is preferably formed by coating. The coating method is not particularly limited and can be appropriately selected from known coating methods according to the purpose, but is performed by spin coating. Preferably, for example, a spin coating method is preferable. In the case of the spin coating method, for example, the rotational speed is about 100 to 10,000 rpm, preferably 800 to 5,000 rpm, the time is about 1 to 10 minutes, and 1 to 90 seconds. preferable.
The application can be performed using a solution (coating solution) containing the resist cover film and a solvent. When the resist cover film forming material contains the amphiphilic substance, the amphiphilic substance is used as a solvent. It is preferable to use a solution obtained by dissolving in a solution.
The solvent is not particularly limited as long as it can dissolve the amphiphile and can be appropriately selected according to the purpose, but preferably contains fluorine. This is advantageous in that the resist cover film can be formed without dissolving the resist film. Examples of the solvent containing fluorine include H-GALDEN (manufactured by Solvay Solexis), FC-77 (manufactured by Sumitomo 3M), and the like. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount with respect to the said resist cover film forming material of the said solvent, Although it can select suitably according to the objective, For example, 0.01-1.0 mass% is preferable, 0.05- 0.2 mass% is more preferable. If the amount used is less than 0.01% by mass, the film formability may be deteriorated such as the occurrence of pinholes. If it exceeds 1.0% by mass, the exposure light is hardly transmitted and the resolution is reduced. May decrease.

The applied resist cover film forming material is preferably baked (heated and dried) during or after the application.
In addition, the conditions and methods for the baking (heating and drying) are not particularly limited as long as the resist film is not softened, and can be appropriately selected according to the purpose. About 150 ° C. is preferable, 80 to 120 ° C. is more preferable, and the time is preferably about 10 seconds to 5 minutes, more preferably 30 seconds to 90 seconds.

  The resist cover film may be formed by exposing the resist film to vapor of the amphiphile in the resist cover film forming material. In this case, since the interaction between the amphiphile and the hydrophilic portion existing on the surface of the film having at least the resist film is promptly performed, the resist cover film can be easily formed.

There is no restriction | limiting in particular as thickness of the said resist cover film | membrane, Although it can select suitably according to the objective, For example, 20 nm or less is preferable and 1-10 nm is more preferable.
If the thickness exceeds 20 nm, the transmittance of ArF excimer laser light or F ₂ excimer laser light may be reduced, and resolution and exposure sensitivity may be reduced. On the other hand, if the thickness is less than 1 nm, defects such as pinholes are likely to occur.
The thickness of the resist cover film is measured, for example, by measuring the absorption intensity of CF stretching vibration using a C _1s spectrum of X-ray photoelectron spectroscopy (ESCA) and an infrared spectrophotometer (“JIR-100”; manufactured by JEOL Ltd.). Can be obtained.

<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 immersion exposure is preferably performed by reduction projection, and a reduction projection lens can be suitably used as the projection lens of the stepper.
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, a liquid containing at least water is preferable, for example, an aqueous cesium chloride solution, water, pure water (refractive index). = 1.44). Among these, pure water 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, in order to obtain a high-definition resist pattern, it is preferable to have a short wavelength of 260 nm or less, and ArF excimer laser light and F ₂ excimer laser light are preferable.

<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, but is preferably one that can dissolve and remove the resist cover film simultaneously with the uncured region of the resist film. Preferable examples include tetramethylammonium hydroxide aqueous solution. By performing development with the developer, the resist cover film is dissolved and removed together with the portion of the resist film not exposed to the exposure light, and a resist pattern is formed (developed).

The development may be performed after removing the resist cover film. In this case, it is preferable to use a stripping solution for removing the resist cover film.
The stripping solution is not particularly limited and can be appropriately selected depending on the purpose. However, a solvent containing at least fluorine is preferable in that the resist cover film can be easily removed. H-GALDEN (manufactured by Solvay Solexis), FC-77 (manufactured by Sumitomo 3M), and the like are preferable.
When performing the development after removing the resist cover film, the developer to be used is not particularly limited and can be appropriately selected from known developers according to the purpose. For example, an alkali developer Can be used.

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 the immersion exposure apparatus 5 described above, and the resist film 2 is irradiated with exposure light (for example, ArF excimer laser light) through the resist cover film 3 in a pattern. To expose. Next, when alkali development 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).

  According to the resist pattern forming method of the present invention, the resist film is effectively protected from the liquid, and the function of the resist film is not impaired, and the occurrence of lens contamination is suppressed and immersion exposure is performed with high precision. Since exposure can be performed and a fine and high-definition resist pattern can be easily and efficiently formed, for example, mask pattern, reticle pattern, magnetic head, LCD (liquid crystal display), PDP (plasma display panel) The present invention can be suitably applied to the manufacture of functional parts such as SAW filters (surface acoustic wave filters), optical parts used for connection of optical wiring, fine parts such as microactuators, semiconductor devices, and the like. It can use suitably for the manufacturing method of an apparatus.

(Method for manufacturing semiconductor device)
The method for manufacturing a semiconductor 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>
The resist pattern forming step is a step of forming a resist pattern on the surface to be processed using the resist pattern forming method of the present invention. That is, after forming a film having at least the resist film, a resist cover film for reducing the surface energy of the exposure target surface by 20 mN / m or more is formed on the film before and after the formation, and the resist cover film is used to form the resist cover film. In this step, the resist film is irradiated with exposure light by immersion exposure and developed to form a resist pattern. By the resist pattern forming step, a resist pattern is formed on the surface to be processed.
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 a semiconductor device and the like, and a substrate such as a silicon wafer or its surface, various oxide films, and the like are preferable. 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 surface 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 a semiconductor device of the present invention, it is possible to perform high-definition exposure by immersion exposure while suppressing the occurrence of lens contamination without impairing the function of the resist film, and a fine and high-definition resist pattern Can be easily and efficiently formed, and high-performance semiconductor devices having a fine wiring pattern formed using the resist pattern, for example, flash memory, DRAM, FRAM, etc., can be mass-produced efficiently.

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

Example 1
-Preparation of resist cover film forming material-
Using a fluorine-containing lubricant (manufactured by Solvay Solexis Co., Ltd.) as a raw material, supercritical extraction with carbon dioxide gas is performed using a supercritical extraction device (“SCF-201”; manufactured by JASCO), and is represented by the following general formula (1). An amphiphilic substance (resist cover film forming material (1)) having an average molecular weight of 4,000 was prepared.

However, in the general formula (1), R has a group represented by the following structural formula (1) and a group represented by the following structural formula (3) in a ratio of 1: 1. m is 30.

-Formation of resist pattern-
A resist material for ArF excimer laser light (“AX5910”; manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated on a silicon substrate to a thickness of 300 nm, and then baked at 110 ° C. for 60 seconds to form a resist film. . Next, on the resist film, a coating solution prepared by dissolving the resist cover film forming material (1) in a fluorine-based solvent (“FC-77”; manufactured by Sumitomo 3M) to a concentration of 0.1% by mass, By spin coating, spin coating was performed at 2,500 rpm for 1 minute. Then, the hydrophilic part in the amphiphile interacted with the resist film surface and was adsorbed on the resist film surface. The resist cover film was formed by baking for 60 seconds on a 110 ° C. hot plate.

Using the C _1s spectrum of X-ray photoelectron spectroscopy (ESCA) and an infrared spectrophotometer (“JIR-100”; manufactured by JEOL Ltd.), the thickness of the obtained resist cover film was measured for the absorption strength of CF stretching vibration. The film thickness was determined to be 1.8 nm.
Further, the surface energy change of the surface to be exposed before and after the formation of the resist cover film was determined by the change in the contact angle measured using a contact angle meter (“CA-QI”; manufactured by Kyowa Interface Science).
The contact angle with respect to pure water of the resist film surface as the exposure target surface before forming the resist cover film was 70 °, and the surface energy was 45 mN / m or more. On the other hand, the contact angle with respect to pure water of the resist cover film surface as the exposure target surface after forming the resist cover film was 112 °, and the surface energy was 20 mN / m or less. Therefore, it was found that the surface energy of the exposure target surface decreased by 25 mN / m or more before and after the formation of the resist cover film, and the exposure target surface was hydrophobized.

The resist film was exposed through the resist cover film using the immersion exposure apparatus (immersion ArF scanner; numerical aperture NA = 0.85), and then baked at 110 ° C. for 60 seconds. Note that water was used as a medium for immersion exposure, and ArF excimer laser light (wavelength 193 nm) was used as exposure light. Next, the resist cover film was removed using a fluorine-based solvent (“H-GALDEN”; manufactured by Solvay Solexis) as a stripping solution. Thereafter, the resist film was subjected to alkali development with an aqueous 2.38 mass% TMAH solution, and the unexposed portion of the resist film was dissolved and removed. As a result, a 70 nm line pattern (resist pattern) was obtained with an exposure dose of 40 mJ / cm ² . In Example 1, when exposure was performed using an exposure apparatus (ArF scanner; numerical aperture NA = 0.85) which is not a liquid immersion type, a 90 nm line pattern was obtained.
In addition, when pure water is dropped on the exposure target surface (resist cover film surface) after the resist cover film is formed and ion chromatography analysis is performed for 10 minutes, elution of contaminants from the resist film is detected. Also, the light intensity after passing through the projection lens was not changed at all even when the above exposure operation was repeated 5000 times, and no lens contamination occurred.

(Comparative Example 1)
In Example 1, a resist pattern was formed in the same manner as in Example 1 except that the resist cover film was not formed. As a result, a 75 nm line pattern (resist pattern) was obtained with an exposure amount of 42 mJ / cm ² .
Moreover, when pure water was dropped on the surface to be exposed (resist film surface) and ion chromatography analysis of pure water was performed for 10 minutes, 1.5% by mass of the acid generator contained in the resist film was found to be in pure water. When the above exposure operation was repeated 5000 times, the light intensity after passing through the projection lens was reduced by 0.5%, and lens contamination occurred.

(Example 2)
As a resist cover film forming material, an amphiphilic substance (resist cover film forming material (2)) having an average molecular weight of 2,600 represented by the following general formula (1) was used.

However, in said general formula (1), R is group represented by following Structural formula (1). m is a mixture of 1 to 3;

-Formation of resist pattern-
A resist material for ArF excimer laser light (“AR1244”; manufactured by JSR) was spin-coated on a silicon substrate to a thickness of 300 nm, and then baked at 115 ° C. for 60 seconds to form a resist film. . Next, on the resist film, the resist cover film forming material (2) is dissolved in a fluorine-based solvent (“H-GALDEN”; manufactured by Solvay Solexis) to prepare a coating solution having a concentration of 0.1% by mass. Was spin-coated by spin coating at 2,000 rpm for 1 minute. Then, the hydrophilic part in the amphiphile interacted with the resist film surface and was adsorbed on the resist film surface. The resist cover film was formed by baking for 60 seconds on a 110 ° C. hot plate.

Using the C _1s spectrum of X-ray photoelectron spectroscopy (ESCA) and an infrared spectrophotometer (“JIR-100”; manufactured by JEOL Ltd.), the thickness of the obtained resist cover film was measured for the absorption strength of CF stretching vibration. The film thickness was determined to be 2.3 nm.
Further, the surface energy change of the surface to be exposed before and after the formation of the resist cover film was determined by the change in the contact angle measured using a contact angle meter (“CA-QI”; manufactured by Kyowa Interface Science).
The contact angle with respect to pure water of the resist film surface as the exposure target surface before forming the resist cover film was 70 °, and the surface energy was 48 mN / m. On the other hand, the contact angle with respect to pure water of the resist cover film surface as the exposure target surface after forming the resist cover film was 112 °, and the surface energy was 18 mN / m. Therefore, it was found that the surface energy of the exposure target surface was reduced by 30 mN / m before and after the formation of the resist cover film, and the exposure target surface was hydrophobized.

The resist film was exposed through the resist cover film using the immersion exposure apparatus (immersion ArF scanner; numerical aperture NA = 0.85), and then baked at 110 ° C. for 60 seconds. Note that water was used as a medium for immersion exposure, and ArF excimer laser light (wavelength 193 nm) was used as exposure light. Next, the resist cover film was removed by spin-off on the resist cover film using a fluorine-based solvent (“H-GALDEN”; manufactured by Solvay Solexis) as the stripping solution. Thereafter, the resist film was subjected to alkali development with an aqueous 2.38 mass% TMAH solution, and the unexposed portion of the resist film was dissolved and removed. As a result, a 65 nm line pattern (resist pattern) was obtained with an exposure amount of 32 mJ / cm ² . In Example 2, when exposure was performed using an exposure apparatus (ArF scanner; numerical aperture NA = 0.85) which is not a liquid immersion type, a line pattern of 85 nm was obtained.
In addition, when pure water is dropped on the exposure target surface (resist cover film surface) after the resist cover film is formed and ion chromatography analysis is performed for 10 minutes, elution of contaminants from the resist film is detected. Also, the light intensity after passing through the projection lens was not changed at all even when the above exposure operation was repeated 5000 times, and no lens contamination occurred.

(Comparative Example 2)
In Example 2, a resist pattern was formed in the same manner as in Example 2 except that the resist cover film was not formed. As a result, a 70 nm line pattern (resist pattern) was obtained at an exposure amount of 34 mJ / cm ² .
Moreover, when pure water was dropped on the surface to be exposed (resist film surface) and ion chromatography analysis was performed for 10 minutes, 3% by mass of the acid generator contained in the resist film was eluted in the pure water. When the above exposure operation was repeated 5000 times, the light intensity after passing through the projection lens was reduced by 1.0%, and the lens was soiled.

(Example 3)
As a resist cover film forming material, an amphiphile having an average molecular weight of 2,000 represented by the following general formula (1) (“fomblin Z-Dol”; manufactured by Solvay Solexis): resist cover film forming material ( 3)) was used.

However, in said general formula (1), R is group represented by following Structural formula (4). m is a mixture of 1 to 3;

-Formation of resist pattern-
A resist material for ArF excimer laser light (“AR1244”; manufactured by JSR) was spin-coated on a silicon substrate to a thickness of 300 nm, and then baked at 115 ° C. for 60 seconds to form a resist film. . Next, the resist cover film forming material (3) was placed in an open container, and the silicon substrate on which the resist film was formed was placed in an oven together with the container, and baked at 90 ° C. for 30 minutes. Then, the vapor of the amphiphile was exposed to the resist film surface, and the hydrophilic portion in the amphiphile was adsorbed on the resist film surface, and a resist cover film was formed.

Using the C _1s spectrum of X-ray photoelectron spectroscopy (ESCA) and an infrared spectrophotometer (“JIR-100”; manufactured by JEOL Ltd.), the thickness of the obtained resist cover film was measured for the absorption strength of CF stretching vibration. The film thickness was determined to be 1.5 nm.
Further, the surface energy change of the surface to be exposed before and after the formation of the resist cover film was determined by the change in contact angle measured using a contact angle meter (“CA-QI”; manufactured by Kyowa Interface Science).
The contact angle with respect to pure water of the resist film surface as the exposure target surface before forming the resist cover film was 70 °, and the surface energy was 48 mN / m. On the other hand, the contact angle with respect to pure water of the resist cover film surface as the exposure target surface after forming the resist cover film was 110 °, and the surface energy was 19 mN / m. Therefore, it was found that the surface energy of the exposure target surface decreased by 29 mN / m before and after the formation of the resist cover film, and the exposure target surface was made hydrophobic.

The resist film was exposed through the resist cover film using the immersion exposure apparatus (immersion ArF scanner; numerical aperture NA = 0.85), and then baked at 110 ° C. for 60 seconds. Note that water was used as a medium for immersion exposure, and ArF excimer laser light (wavelength 193 nm) was used as exposure light. Next, the resist cover film was removed by spin-off on the resist cover film using a fluorine-based solvent (“H-GALDEN”; manufactured by Solvay Solexis) as the stripping solution. Thereafter, the resist film was subjected to alkali development with an aqueous 2.38 mass% TMAH solution, and the unexposed portion of the resist film was dissolved and removed. As a result, a 65 nm line pattern (resist pattern) was obtained with an exposure amount of 32 mJ / cm ² . In Example 3, when exposure was performed using a non-immersion exposure apparatus (ArF scanner; numerical aperture NA = 0.85), a line pattern of 85 nm was obtained.
In addition, when pure water is dropped on the exposure target surface (resist cover film surface) after the resist cover film is formed and ion chromatography analysis is performed for 10 minutes, elution of contaminants from the resist film is detected. Further, the light intensity after passing through the projection lens was not changed at all even when the above exposure operation was repeated 5000 times, and no lens contamination occurred.

(Comparative Example 3)
In Example 3, a resist pattern was formed in the same manner as in Example 3 except that the resist cover film was not formed. As a result, a 70 nm line pattern (resist pattern) was obtained at an exposure amount of 34 mJ / cm ² .
Moreover, when pure water was dropped on the surface to be exposed (resist film surface) and ion chromatography analysis of pure water was performed for 10 minutes, 1.5% by mass of the acid generator contained in the resist film was found to be in pure water. The light intensity after passing through the projection lens decreased by 1.0%, and the lens was soiled.

  Table 1 shows the resolution, contact angle before and after the formation of the resist cover film, exposure target surface energy, resolution (pattern size), and presence or absence of elution of the resist component for each of the obtained resist patterns.

  In Table 1, in Examples 1 to 3, since the resist cover film was formed on the resist film, the surface energy of the exposure target surface was lowered, the exposure target surface was hydrophobized, and the resist cover film was passed through the resist cover film. In addition, it was found that when the resist film was subjected to immersion exposure, the resist component was not eluted and the lens contamination of the projection lens did not occur, and a fine, high-definition resist pattern with excellent resolution was obtained. On the other hand, in Comparative Examples 1 to 3, since the resist cover film was not formed in Examples 1 to 3, the resist component was eluted, causing lens contamination of the projection lens, resist characteristic deterioration, and lens contamination. As a result, the resolution was lowered, and it was found that a high-definition resist pattern could not be obtained.

Example 4
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 4, the resist pattern 14 was manufactured in the same manner as in Examples 1 to 3 by performing immersion exposure using the resist cover film formed of the resist cover film forming material of the present invention. It is a resist pattern.

(Example 5)
-Flash memory and its manufacture-
Example 5 is an example of a method of manufacturing a semiconductor device 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 to 4 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 cell electrode 31a / capacitor insulating film 30c / floating gate electrode 28c in the memory cell portion (left and center diagrams in FIG. 23) as a mask, the dose of 1 × 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 6)
-Manufacture of magnetic heads-
Example 6 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 6, the following resist patterns 102 and 126 were 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.

The preferred embodiments of the present invention are as follows.
(Additional remark 1) After forming the film which has at least a resist film on a to-be-processed surface, the resist cover film formation material which reduces the surface energy of the surface for exposure by 20 mN / m or more on this film before and after formation of the resist cover film A resist pattern forming method, comprising: forming a resist cover film using the substrate, irradiating the resist film with exposure light by immersion exposure through the resist cover film, and developing the resist film.
(Additional remark 2) The formation method of the resist pattern of Additional remark 1 whose surface energy of the exposure object surface after resist cover film formation is 30 mN / m or less.
(Supplementary note 3) The method for forming a resist pattern according to any one of supplementary notes 1 to 2, wherein the resist cover film forming material contains at least an amphiphilic substance.
(Supplementary note 4) The method for forming a resist pattern according to any one of supplementary notes 1 to 3, wherein the formation of the resist cover film is performed by causing a resist cover film forming material to interact with the surface of the film having at least the resist film.
(Additional remark 5) The formation method of the resist pattern of Additional remark 4 whose interaction is at least any one of chemical adsorption and physical adsorption.
(Supplementary note 6) The method for forming a resist pattern according to any one of supplementary notes 3 to 5, wherein the amphiphilic substance is a compound containing at least fluorine.
(Supplementary note 7) The method for forming a resist pattern according to any one of supplementary notes 3 to 6, wherein the amphiphilic substance has at least a polar group.
(Supplementary note 8) The method for forming a resist pattern according to supplementary note 7, wherein the amphiphilic substance is a linear compound and has a polar group at least at one end of the linear chain.
(Supplementary note 9) The method for forming a resist pattern according to any one of supplementary notes 3 to 8, wherein the amphiphilic substance is represented by the following general formula (1).
In the general formula (1), R may be the same as or different from each other, and is a group represented by any one of the following structural formulas (1) to (3). m represents an integer of 1 or more.
However, in the structural formula (2), n represents an integer of 1 or more.
(Additional remark 10) The formation method of the resist pattern in any one of additional remarks 1-9 in which a resist film contains an acid generator at least.
(Supplementary note 11) The method for forming a resist pattern according to any one of supplementary notes 1 to 10, wherein the film having at least a resist film has an antireflection film on the resist film.
(Supplementary note 12) Any one of Supplementary notes 1 to 11, 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. Of forming a resist pattern.
(Additional remark 13) The formation method of the resist pattern in any one of additional remarks 1-12 whose refractive index of the liquid used for immersion exposure is larger than one.
(Additional remark 14) The formation method of the resist pattern of Additional remark 13 in which a liquid contains water at least.
(Supplementary note 15) The resist pattern forming method according to any one of supplementary notes 1 to 14, wherein the immersion exposure is performed by reduction projection.
(Supplementary note 16) The method for forming a resist pattern according to any one of supplementary notes 1 to 15, wherein the thickness of the resist cover film is 20 nm or less.
(Appendix 17) The resist cover film is formed by applying a solution obtained by dissolving an amphiphile in a solvent onto a film having at least a resist film. A method for forming a resist pattern.
(Supplementary note 18) The method for forming a resist pattern according to supplementary note 17, wherein the solvent contains fluorine.
(Appendix 19) The method for forming a resist pattern according to any one of appendices 3 to 16, wherein the resist cover film is formed by exposing a film having at least the resist film to an amphiphilic substance vapor.
(Supplementary note 20) The resist pattern forming method according to any one of supplementary notes 1 to 19, wherein the development is performed after the removal of the resist cover film.
(Supplementary note 21) The method for forming a resist pattern according to supplementary note 20, wherein the removal of the resist cover film is performed using a solvent containing at least fluorine.
(Appendix 22) A resist pattern forming step of forming a resist pattern on the processing surface using the resist pattern forming method according to any one of Appendixes 1 to 21, and the processing by etching using the resist pattern as a mask And a patterning step of patterning the surface.
(Supplementary note 23) A semiconductor device manufactured by the method for manufacturing a semiconductor device according to supplementary note 22.
(Supplementary Note 24) Used to form a resist cover film that covers the resist film when immersion exposure is performed on the resist film, and the surface energy of the exposure target surface is 20 mN / second before and after the formation of the resist cover film. A resist cover film forming material characterized by being lowered by m or more.
(Additional remark 25) The resist cover film forming material of Additional remark 24 whose surface energy of the exposure object surface after resist cover film formation is 30 mN / m or less.

Since the resist cover film forming material of the present invention imparts hydrophobicity by reducing the surface energy of the exposure target surface before and after the formation of the resist cover film, the refractive index n is 1 between the projection lens of the exposure apparatus and the wafer. In immersion exposure technology that improves resolution by filling a medium (liquid) larger than (refractive index of air), it can be suitably used as a resist cover film for immersion exposure that protects the resist film from the liquid It is.
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 manufacture of optical components used for connection, microparts such as microactuators, semiconductor devices, and the like, and can be preferably used in the method of manufacturing a semiconductor device of the present invention.
The method for manufacturing a semiconductor device of the present invention can be suitably used for manufacturing the semiconductor device of the present invention. The semiconductor device of the present invention can be suitably used in the field 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 a semiconductor device of 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 a semiconductor 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 view for explaining an example of a method for manufacturing a semiconductor 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 a semiconductor 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 a semiconductor 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 view for explaining an example of the method for manufacturing a semiconductor device of 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 a semiconductor 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 a semiconductor 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 a semiconductor 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 method for manufacturing a semiconductor device of the present invention. FIG. 15 is a plan view showing a first example of a FLASH EPROM manufactured by the method for manufacturing a semiconductor device 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 a semiconductor 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 a semiconductor device of the present invention, and represents the next step of FIG. FIG. 18 is a schematic explanatory view of a first example of the manufacture of a FLASH EPROM by the method for manufacturing a semiconductor 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 a semiconductor device of the present invention, and represents the next step of FIG. FIG. 20 is a schematic explanatory view of a first example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 21 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 22 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 23 is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor 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 a semiconductor device of the present invention, and represents the next step of FIG. FIG. 25 is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention. FIG. 26 is a schematic explanatory view of a second example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 27 is a schematic explanatory diagram of a second example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device of the present invention, and represents the next step of FIG. FIG. 28 is a schematic explanatory diagram of a third example of manufacturing a FLASH EPROM by the method for manufacturing a semiconductor device of the present invention. FIG. 29 is a schematic explanatory view of a third example of the manufacture of FLASH EPROM by the method for manufacturing a semiconductor device 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 FLASH EPROM by the method for manufacturing a semiconductor device 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 (5)

After forming a film having at least a resist film on the surface to be processed, a resist is formed on the film using a resist cover film forming material that reduces the surface energy of the exposure target surface by 20 mN / m or more before and after the formation of the resist cover film. Forming a cover film, irradiating the resist film with immersion light through the resist cover film by immersion exposure, and developing, wherein the resist cover film forming material includes at least an amphiphilic substance. The method for forming a resist pattern, wherein the amphiphilic substance is represented by the following general formula (1).
In the general formula (1), R may be the same as or different from each other, and is a group represented by any one of the following structural formulas (1) to (3). m represents an integer of 1 or more.
However, in the structural formula (2), n represents an integer of 1 or more.   The resist cover film is formed by causing a resist cover film forming material to interact with the surface of the film having at least the resist film, and the interaction is at least one of chemical adsorption and physical adsorption. The resist pattern forming method described.   The resist pattern according to any one of claims 1 to 2, wherein the resist cover film is formed by applying a solution obtained by dissolving the amphiphile in a solvent on a film having at least a resist film. Forming method.   The method for forming a resist pattern according to claim 3, wherein the amphiphilic substance is a compound containing at least fluorine. At least an amphiphilic substance is included, and the amphiphilic substance is represented by the following general formula (1), and forms a resist cover film that covers the resist film when immersion exposure is performed on the resist film. A resist cover film forming material characterized in that the surface energy of the surface to be exposed is reduced by 20 mN / m or more before and after the formation of the resist cover film.

In the general formula (1), R may be the same as or different from each other, and is a group represented by any one of the following structural formulas (1) to (3). m represents an integer of 1 or more.

However, in the structural formula (2), n represents an integer of 1 or more.