JP4447569B2 - Resist pattern thickening material, resist pattern forming method, and semiconductor device manufacturing method - Google Patents

Description

  The present invention relates to a resist pattern thickening material which can be applied on a resist pattern to thicken the resist pattern and form a fine resist omission pattern exceeding the exposure limit of a light source of an existing exposure apparatus, and The present invention relates to a method for forming a resist pattern using a semiconductor and a method for manufacturing a semiconductor device.

Currently, high integration of semiconductor integrated circuits is progressing, and LSI and VLSI have been put into practical use, and accordingly, the wiring pattern extends to an area of 0.2 μm or less and the minimum pattern reaches 0.1 μm or less. To form a fine wiring pattern, a substrate to be processed on which a thin film is formed is covered with a resist film, subjected to selective exposure and developed to form a resist pattern, and then dry etching is performed using the resist pattern as a mask. A lithography technique that obtains a desired pattern by removing the resist pattern is very important.
The formation of a fine wiring pattern requires both the shortening of the wavelength of the light source in the exposure apparatus and the development of a resist material having a high resolution according to the characteristics of the light source. However, in order to reduce the wavelength of the light source in the exposure apparatus, it is necessary to update the exposure apparatus that requires enormous costs. On the other hand, it is not easy to develop a resist material to cope with exposure using a short wavelength light source.

  In the manufacturing process of a semiconductor device, a fine resist removal pattern is formed by a resist pattern, and then fine patterning is performed using the resist pattern as a mask. Therefore, the resist pattern has excellent etching resistance. It is desirable. However, the ArF excimer laser exposure technology, which is the latest technology, has a problem that the resist material used has insufficient etching resistance. Therefore, it is conceivable to use a KrF resist having excellent etching resistance, but the etching resistance is insufficient when the etching conditions are severe, the layer to be processed is thick, the fine pattern is formed, or the resist is thin. There is a demand for the development of a technique capable of forming a resist pattern with excellent etching resistance and forming a fine resist omission pattern using the resist pattern.

It should be noted that, by using KrF (krypton fluoride) excimer laser light (wavelength 248 nm), which is the deep ultraviolet ray, as the exposure light for the resist, a resist removal pattern refinement technique called RELACS that can form a fine removal pattern Has been proposed (see, for example, Patent Document 1). This technique uses a KrF (krypton fluoride) excimer laser (wavelength 248 nm) as the exposure light to form a resist pattern by exposing the resist (positive type or negative type), and then forms a water-soluble resin composition. A coating film is provided so as to cover the resist pattern, and the coating film and the resist pattern are allowed to interact with each other using the residual acid in the resist pattern material at the interface to thicken the resist pattern. (Hereinafter sometimes referred to as “swelling”), the distance between the resist patterns is shortened to form a fine resist omission pattern.
However, in this case, since the KrF resist to be used strongly absorbs ArF excimer laser light, the ArF excimer laser light cannot pass through the KrF resist, and the ArF excimer laser light cannot be used as the exposure light. There is.
From the viewpoint of forming a fine wiring pattern, it is desirable that ArF excimer laser light having a shorter wavelength than KrF excimer laser light can be used as a light source in the exposure apparatus.
Therefore, ArF excimer laser light can also be used as a light source for the exposure apparatus during patterning, and no technology capable of forming a fine resist removal pattern has yet been provided.

Japanese Patent Laid-Open No. 10-73927

An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention can use a light source such as ArF excimer laser light in an existing exposure apparatus as it is when patterning a resist pattern, is excellent in mass productivity, has no dependency on the material and size of the resist pattern, and has a resist missing pattern. An object of the present invention is to provide a method for forming a resist pattern that can be finely formed exceeding the exposure limit of the light source.
In addition, the present invention has no dependency on the material and size of the resist pattern, and when applied to the resist pattern, the resist pattern can be thickened efficiently, exceeding the exposure limit of the light source of the existing exposure apparatus. An object of the present invention is to provide a resist pattern thickening material suitable for producing a fine resist omission pattern.
In addition, the present invention makes it possible to form a fine pattern in an underlayer such as an oxide film by using a finely formed resist removal pattern, and to efficiently mass-produce high-performance semiconductor devices having fine wiring and the like. An object of the present invention is to provide a method for manufacturing a possible semiconductor device.

Means for solving the above-described problems are as listed in the appendix to be described later.
The resist pattern thickening material of the present invention is characterized by containing a resin and a surfactant. When the resist pattern thickening material is applied onto the resist pattern, the applied resist pattern thickening material permeates the resist pattern near the interface with the resist pattern. At this time, since the affinity between the resist pattern thickening material and the resist pattern is good, a surface layer formed by integrating the resist pattern thickening material and the resist pattern on the surface of the resist pattern Is efficiently formed (the resist pattern is efficiently thickened by the resist pattern thickening material). Since the resist pattern thus formed (hereinafter sometimes referred to as “thickened resist pattern”) is thickened by the resist pattern thickening material, the omission formed by the thickened resist pattern. The pattern has a finer structure beyond the exposure limit.

  The resist pattern forming method of the present invention is a method of forming a resist pattern, and then applying the resist pattern thickening material of the present invention so as to cover the surface of the resist pattern, thereby increasing the thickness of the resist pattern. A resist pattern is formed. In the method for forming a resist pattern of the present invention, when the resist pattern thickening material is applied onto the formed resist pattern, the interface with the resist pattern among the applied resist pattern thickening material. Things in the vicinity soak into the resist pattern. For this reason, the resist pattern thickening material and the resist pattern are integrated on the surface of the resist pattern, and the resist pattern is thickened. Since the thickened resist pattern formed in this way is thickened by the resist pattern thickening material, the resist omission pattern formed by the thickened resist pattern is finer beyond the exposure limit. It has a structure.

  In the method for manufacturing a semiconductor device of the present invention, after forming a resist pattern on an underlayer, the resist pattern thickening material of the present invention is applied so as to cover the surface of the resist pattern, thereby thickening the resist pattern. A thickened resist pattern forming step for forming a thickened resist pattern, and a patterning step for patterning the underlayer by etching using the thickened resist pattern. In the method for manufacturing a semiconductor device of the present invention, after a resist pattern is formed on an underlayer, the resist pattern thickening material is applied onto the resist pattern. Then, among the applied resist pattern thickening material, the material near the interface with the resist pattern soaks into the resist pattern. Therefore, on the surface of the resist pattern, the resist pattern thickening material and the resist pattern are integrated, and the resist pattern is thickened. Since the thickened resist pattern formed in this way is thickened by the resist pattern thickening material, the resist omission pattern formed by the thickened resist pattern is finer beyond the exposure limit. It has a structure. Then, since the base layer is patterned by etching using the pattern as a mask, a high-quality and high-performance semiconductor device having an extremely fine pattern is efficiently manufactured.

According to the present invention, the conventional problems can be solved in response to the demand.
In addition, according to the present invention, a light source such as ArF excimer laser light in an existing exposure apparatus can be used as it is when patterning a resist pattern, and it is excellent in mass productivity, and a resist omission pattern is finely formed exceeding the exposure limit of the light source. A possible resist pattern forming method can be provided.
Further, according to the present invention, when applied to a resist pattern, the resist pattern can be efficiently thickened, which is suitable for producing a fine resist omission pattern that exceeds the exposure limit of the light source of an existing exposure apparatus. A resist pattern thickening material can be provided.
In addition, according to the present invention, a fine pattern can be formed on a base layer such as an oxide film by using a finely formed resist removal pattern as a mask pattern, and a high-performance semiconductor device having fine wiring and the like can be obtained. A method of manufacturing a semiconductor device that can be efficiently mass-produced can be provided.

(Resist pattern thickening material)
The resist pattern thickening material of the present invention contains a resin and a surfactant, and further contains a cyclic structure compound, an organic solvent, other components, etc., appropriately selected as necessary. .

The resist pattern thickening material of the present invention is water-soluble or alkali-soluble.
The resist pattern thickening material of the present invention may be in the form of an aqueous solution, a colloidal liquid, an emulsion, or the like, but is preferably an aqueous solution.

-Resin-
The resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably water-soluble or alkali-soluble.
The said resin may be used individually by 1 type, and may use 2 or more types together.

When the resin is a water-soluble resin, the water-soluble resin preferably has a water solubility of 0.1 g or more in water at 25 ° C., and more preferably has a water solubility of 0.3 g or more. A water-soluble one that dissolves 0.5 g or more is particularly preferable.
Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyacrylic acid, polyvinyl pyrrolidone, polyethyleneimine, polyethylene oxide, styrene-maleic acid copolymer, polyvinylamine, polyallylamine, and an oxazoline group-containing water-soluble resin. Examples thereof include resins, water-soluble melamine resins, water-soluble urea resins, alkyd resins, and sulfonamide resins.

When the resin is alkali-soluble, the alkali-soluble resin is preferably an alkali-soluble resin that dissolves 0.1 g or more in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. Those exhibiting alkali solubility capable of dissolving 3 g or more are more preferable, and those exhibiting alkali solubility capable of dissolving 0.5 g or more are particularly preferable.
Examples of the alkali-soluble resin include novolak resins, vinylphenol resins, polyacrylic acid, polymethacrylic acid, poly p-hydroxyphenyl acrylate, poly p-hydroxyphenyl methacrylate, and copolymers thereof.

In the present invention, the resin may be a resin having at least a part of a cyclic structure.
In this case, the cyclic structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a structure selected from at least one of an aromatic compound, an alicyclic compound, and a heterocyclic compound is used. Preferably mentioned.

  Examples of the aromatic compounds include polyhydric phenol compounds, polyphenol compounds, aromatic carboxylic acid compounds, naphthalene polyhydric alcohol compounds, benzophenone compounds, flavonoid compounds, porphine, water-soluble phenoxy resins, aromatic-containing water-soluble dyes, and the like. Derivatives thereof, glycosides thereof, and the like. These may be used alone or in combination of two or more.

  Examples of the polyhydric phenol compound include resorcin, resorcin [4] arene, pyrogallol, gallic acid, derivatives or glycosides thereof, and the like.

  Examples of the polyphenol compound and derivatives thereof include catechin, anthocyanidin (pelargosine type (4′-hydroxy), cyanidin type (3 ′, 4′-dihydroxy), delphinidin type (3 ′, 4 ′, 5′-trihydroxy). )), Flavan-3,4-diol, proanthocyanidins, derivatives or glycosides thereof, and the like.

  Examples of the aromatic carboxylic acid compound and derivatives thereof include salicylic acid, phthalic acid, dihydroxybenzoic acid, tannin, derivatives and glycosides thereof, and the like.

  Examples of the naphthalene polyhydric alcohol compound and derivatives thereof include naphthalenediol, naphthalenetriol, derivatives or glycosides thereof, and the like.

  Examples of the benzophenone compound and derivatives thereof include alizarin yellow A, derivatives or glycosides thereof, and the like.

  Examples of the flavonoid compound and derivatives thereof include flavone, isoflavone, flavanol, flavonone, flavonol, flavan-3-ol, aurone, chalcone, dihydrochalcone, quercetin, derivatives or glycosides thereof, and the like.

Examples of the alicyclic compound include polycycloalkanes, cycloalkanes, condensed rings, derivatives thereof, glycosides thereof, and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polycycloalkanes include norbornane, adamantane, norpinane, and sterane.
Examples of the cycloalkanes include cyclopentane and cyclohexane.
Examples of the condensed ring include steroids.

  Examples of the heterocyclic compound include nitrogen-containing cyclic compounds such as pyrrolidine, pyridine, imidazole, oxazole, morpholine, and pyrrolidone, oxygen-containing cyclic compounds such as polysaccharides including furan, pyran, pentose, and hexose. Etc. are preferable.

Among the resins having at least a part of the cyclic structure, those having two or more polar groups are preferable in that they are excellent in at least one of water solubility and alkali solubility.
There is no restriction | limiting in particular as said polar group, Although it can select suitably according to the objective, For example, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfonyl group etc. are mentioned.

  Further, in the case of a resin having at least a part of the cyclic structure, the resin portion other than the cyclic structure is not particularly limited as long as the entire resin is water-soluble or alkaline, and can be appropriately selected according to the purpose. Examples thereof include water-soluble resins such as polyvinyl alcohol and polyvinyl acetal described above, and alkali-soluble resins such as novolac resin and vinyl phenol resin.

When the resin has the cyclic structure in at least a part thereof, the molar content of the cyclic structure is not particularly limited and can be appropriately selected according to the purpose, but requires high etching resistance. In this case, it is preferably 5 mol% or more, more preferably 10 mol% or more.
In addition, the said molar content rate can be measured using NMR etc., for example.

  The content of the resin in the resist pattern thickening material varies depending on the amount of a surfactant and the like to be described later, and cannot be specified unconditionally, but can be appropriately determined according to the purpose.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, nonionic surfactants are preferable in that they do not contain metal ions.

  The nonionic surfactant is preferably selected from an alkoxylate surfactant, a fatty acid ester surfactant, an amide surfactant, an alcohol surfactant, and an ethylenediamine surfactant. Can be mentioned. Specific examples of these include polyoxyethylene-polyoxypropylene condensate compounds, polyoxyalkylene alkyl ether compounds, polyoxyethylene alkyl ether compounds, polyoxyethylene derivative compounds, sorbitan fatty acid ester compounds, glycerin fatty acid ester compounds, Primary alcohol ethoxylate compound, phenol ethoxylate compound, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, Secondary alcohol ethoxylates and the like can be mentioned.

  The cationic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkyl cationic surfactants, amide type quaternary cationic surfactants, and ester type quaternary cationic types. Surfactant etc. are mentioned.

  There is no restriction | limiting in particular as said amphoteric surfactant, According to the objective, it can select suitably, For example, an amine oxide type surfactant, a betaine type surfactant, etc. are mentioned.

  The content of the above surfactant in the resist pattern thickening material differs depending on the type and content of the resin and the like and cannot be specified unconditionally, but can be appropriately selected according to the purpose. it can.

-Cyclic structure compound-
It is preferable that the resist pattern thickening material further contains the cyclic structure compound because the etching resistance of the resulting resist pattern (thickening resist pattern) can be remarkably improved.
The cyclic structure-containing compound is not particularly limited as long as it contains a cyclic structure, and can be appropriately selected according to the purpose. However, not only the compound but also a resin is included, and it is water-soluble and alkali-soluble. Is preferred.

In the case where the cyclic structure-containing compound is water-soluble, as the water-solubility, for example, a water-soluble one that dissolves 0.1 g or more in 100 g of water at 25 ° C. is preferable, and water-solubility that dissolves 0.3 g or more. Are more preferable, and those exhibiting water solubility capable of dissolving 0.5 g or more are particularly preferable.
When the cyclic structure compound is alkali-soluble, the alkali-solubility is, for example, an alkali-soluble compound that dissolves 0.1 g or more in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. More preferably, 0.3 g or more soluble alkali soluble is more preferable, 0.5 g or more soluble alkali soluble is particularly preferable.

  Preferred examples of the cyclic structure compound include aromatic compounds, alicyclic compounds, and heterocyclic compounds. The contents of these compounds are as described above, and preferable ones among them are also as described above.

Among the cyclic structure-containing compounds, those having two or more polar groups are preferable, those having three or more are more preferable, and those having four or more are particularly preferable in that they are excellent in at least one of water solubility and alkali solubility.
There is no restriction | limiting in particular as said polar group, Although it can select suitably according to the objective, For example, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfonyl group etc. are mentioned.

When the cyclic structure compound is a resin, the molar content of the cyclic structure with respect to the resin is not particularly limited and can be appropriately selected according to the purpose, but when high etching resistance is required. Is preferably 5 mol% or more, more preferably 10 mol% or more.
In addition, the said molar content rate can be measured using NMR etc., for example.

  The content of the cyclic structure compound in the resist pattern thickening material can be appropriately determined according to the type and content of the resin and the like.

-Organic solvent-
When the organic solvent is contained in the resist pattern thickening material, the solubility of the resin, the surfactant, etc. in the resist pattern thickening material can be improved.

  The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol-based organic solvents, chain ester-based organic solvents, cyclic ester-based organic solvents, ketone-based organic solvents, and chain ethers. And organic ether solvents and cyclic ether organic solvents.

Examples of the alcohol organic solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, and the like.
Examples of the chain ester organic solvent include ethyl lactate and propylene glycol methyl ether acetate (PGMEA).
Examples of the cyclic ester organic solvent include lactone organic solvents such as γ-butyrolactone.
Examples of the ketone organic solvent include ketone organic solvents such as acetone, cyclohexanone, and heptanone.
Examples of the chain ether organic solvent include ethylene glycol dimethyl ether.
Examples of the cyclic ether include tetrahydrofuran, dioxane, and the like.

  These organic solvents may be used individually by 1 type, and may use 2 or more types together. Among these, the thing which has a boiling point of about 80-200 degreeC is preferable at the point which can thicken finely.

  The content of the organic solvent in the resist pattern thickening material can be appropriately determined according to the type and content of the resin and the surfactant.

-Other ingredients-
The other components are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected according to the purpose. Various known additives such as crosslinking agents, thermal acid generators, amines, Preferable examples include quenchers such as amides and ammonium chlorine.
The content of the other components in the resist pattern thickening material can be appropriately determined according to the type and content of the resin and the surfactant.

-Use etc.-
The resist pattern thickening material of the present invention can be used by coating on the resist pattern.
In addition, at the time of the application, the surfactant may not be contained in the resist pattern thickening material but may be separately applied before applying the resist pattern thickening material.

When the resist pattern thickening material is applied onto the resist pattern, the resist pattern is thickened to form a thickened resist pattern.
The diameter or width (opening dimension) of the resist removal pattern formed by the thickened resist pattern thus obtained is smaller than the diameter or width of the resist removal pattern formed by the resist pattern. A finer resist omission pattern is formed beyond the exposure limit of the light source of the exposure apparatus used when patterning the resist pattern. For example, when ArF excimer laser light is used when patterning the resist pattern, the resulting resist pattern is thickened using the resist pattern thickening material of the present invention to form a thickened resist pattern. Then, the resist omission pattern formed by the thickened resist pattern provides a fine resist omission pattern similar to that obtained when patterning using an electron beam.
At this time, the thickness of the resist pattern can be controlled within a desired range by appropriately adjusting the viscosity, coating thickness, baking temperature, baking time, and the like of the resist pattern thickening material. .

-Resist pattern material-
The material of the resist pattern (the resist pattern to which the resist pattern thickening material of the present invention is applied) is not particularly limited and can be appropriately selected from known resist materials according to the purpose. For example, g-line resist, i-line resist, KrF resist, ArF that can be patterned with g-line, i-line, KrF excimer laser, ArF excimer laser, F2 excimer laser, electron beam, etc. A resist, an F2 resist, an electron beam resist and the like are preferable. These may be chemically amplified or non-chemically amplified. Among these, KrF resist, ArF resist, etc. are preferable, and ArF resist is more preferable.
Specific examples of the resist pattern 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 pattern forming method, size, thickness, and the like are not particularly limited and can be appropriately selected according to the purpose. In particular, the thickness is appropriately determined depending on the substrate to be processed, etching conditions, and the like. However, it is generally about 0.2 to 200 μm.

The thickening of the resist pattern using the resist pattern thickening material of the present invention will be described below with reference to the drawings.
As shown in FIG. 1A, after forming a resist pattern 3 on an underlayer (base material) 5, a resist pattern thickening material 1 is applied to the surface of the resist pattern 3 and prebaked (heated and dried). ) To form a coating film. Then, as shown in FIG. 1 (b), the resist pattern thickening material 1 is mixed (impregnated) into the resist pattern 3 at the interface between the resist pattern 3 and the resist pattern thickening material 1, and the inner layer resist pattern The surface layer 10a is formed by mixing (impregnating) at the interface between 10b (resist pattern 3) and the resist pattern thickening material 1.
Thereafter, as shown in FIG. 1 (c), by performing development processing, a portion of the applied resist pattern thickening material 1 that is not mixed with the resist pattern 3 is dissolved and removed, and the thickness is increased. A thickened resist pattern 10 is formed (developed).
The development treatment may be water development or development with an alkaline developer.

  The thickened resist pattern 10 has a surface layer 10a formed by mixing the resist pattern thickening material 1 on the surface of the resist pattern 10b (resist pattern 3). Since the thickened resist pattern 10 is thicker than the resist pattern 3 by the thickness of the surface layer 10a, the width of the resist removal pattern formed by the thickened resist pattern 10 is formed by the resist pattern 3. It is smaller than the width of the resist omission pattern. For this reason, the resist omission pattern can be finely formed exceeding the exposure limit of the light source in the exposure apparatus when forming the resist pattern 3, and the resist omission pattern formed by the thickened resist pattern 10 is the resist pattern. It is finer than the resist omission pattern formed by 3b.

  The surface layer 10 a in the thickened resist pattern 10 is formed of the resist pattern thickening material 1. In the case where the resist pattern thickening material 1 contains at least one of the cyclic structure compound and the resin having a cyclic structure in part, the resist pattern 3 (resist pattern 10b) is inferior in etching resistance. Even so, the resulting thickened resist pattern 10 has a surface layer 10a containing at least one of the water-soluble cyclic structure compound and the resin partly having the cyclic structure on its surface, so that etching resistance is obtained. Remarkably superior.

-Use-
The resist pattern thickening material of the present invention can be suitably used to thicken a resist pattern and to refine a resist omission pattern beyond the exposure limit. Moreover, the resist pattern thickening material of the present invention can be used particularly preferably in the method for manufacturing a semiconductor device of the present invention.
In addition, when the resist pattern thickening material of the present invention contains at least one of the cyclic structure compound and the resin partly having the cyclic structure, it is exposed to plasma or the like, and is subjected to etching resistance on the surface. Can be suitably used for coating or thickening a pattern formed of a resin or the like that needs to be improved, and has a part of the water-soluble cyclic structure compound and cyclic structure as a material of the pattern. When at least one of the formed resins cannot be used, it can be used more suitably.

(Method for forming resist pattern)
In the resist pattern forming method of the present invention, after the resist pattern is formed, the resist pattern thickening material of the present invention is applied so as to cover the surface of the resist pattern, and the resist pattern is thickened. A resist pattern is formed.

Suitable examples of the resist pattern material include those described above in the resist pattern thickening material of the present invention.
The resist pattern can be formed according to a known method.
The resist pattern can be formed on a base (base material), and the base (base material) is not particularly limited and may be appropriately selected depending on the intended purpose. In the case of being formed, the substrate (base material) usually preferably includes a substrate such as a silicon wafer, various oxide films, and the like.

The method for applying the resist pattern thickening material is not particularly limited, and can be appropriately selected from known application methods according to the purpose. For example, a spin coating method is preferably used. In the case of the spin coating method, the conditions are, for example, a rotational speed of about 100 to 10,000 rpm, preferably 800 to 5,000 rpm, a time of about 1 second to 10 minutes, and preferably 1 to 90 seconds. .
The coating thickness at the time of the coating is usually about 100 to 10,000 mm (10 to 1,000 nm), preferably about 2,000 to 5,000 mm (200 to 500 nm).
In addition, at the time of the application, the surfactant may not be contained in the resist pattern thickening material but may be separately applied before applying the resist pattern thickening material.

Pre-baking (heating and drying) the applied resist pattern thickening material during or after the application is performed at the interface between the resist pattern and the resist pattern thickening material. This is preferable in that mixing (impregnation) of the material into the resist pattern can be efficiently generated.
The pre-baking (heating / drying) conditions and method are not particularly limited as long as the resist pattern is not softened, and can be appropriately selected according to the purpose. For example, the temperature is 40 to 120 ° C. 70 to 100 ° C is preferable, the time is about 10 seconds to 5 minutes, and 40 seconds to 100 seconds is preferable.

In addition, baking the applied resist pattern thickening material after the pre-baking (heating / drying) effectively performs the mixing at the interface between the resist pattern and the resist pattern thickening material. This is preferable in that it can be advanced.
The baking conditions and method are not particularly limited and may be appropriately selected depending on the intended purpose. However, usually higher temperature conditions than the pre-baking (heating / drying) are employed. As conditions for the baking, for example, the temperature is about 70 to 150 ° C., preferably 90 to 130 ° C., the time is about 10 seconds to 5 minutes, and preferably 40 seconds to 100 seconds.

Furthermore, it is preferable that after the baking, the applied resist pattern thickening material is developed. In this case, it is preferable in that the thickened resist pattern can be developed (obtained) by dissolving and removing a portion of the applied resist pattern thickening material that is not mixed with the resist pattern.
The development processing is as described above.

Here, the resist pattern forming method of the present invention will be described below with reference to the drawings.
As shown in FIG. 2 (a), after applying a resist material 3a on the base layer (base material) 5, after patterning this to form a resist pattern 3 as shown in FIG. 2 (b), As shown in FIG. 2C, the resist pattern thickening material 1 is applied to the surface of the resist pattern 3 and prebaked (heated and dried) to form a coating film. Then, the resist pattern thickening material 1 is mixed (impregnated) into the resist pattern 3 at the interface between the resist pattern 3 and the resist pattern thickening material 1, and as shown in FIG. The mixing (impregnation) layer is formed at the interface between the resist pattern thickening material 1 and the resist pattern thickening material 1. Thereafter, as shown in FIG. 2 (e), when development processing is performed, a portion of the applied resist pattern thickening material 1 that is not mixed with the resist pattern 3 is dissolved and removed, and a resist pattern 10b (resist A thickened resist pattern 10 having a surface layer 10a on the pattern 3) is formed (developed).
The development processing may be water development or development with an alkaline aqueous solution, but water development is preferable in that the development processing can be efficiently performed at low cost.

  The thickened resist pattern 10 has a surface layer 10a formed by mixing the resist pattern thickening material 1 on the surface of the resist pattern 10b (resist pattern 3). Since the resist pattern 10 is thickened by the thickness of the surface layer 10a compared to the resist pattern 3 (resist pattern 10b), the width of the resist removal pattern formed by the thickened resist pattern 10 is the resist pattern 3 The resist missing pattern formed by the thickened resist pattern 10 is finer than the width of the resist missing pattern formed by (resist pattern 10b).

  The surface layer 10a in the thickened resist pattern 10 is formed of the resist pattern thickening material 1, and the resist pattern thickening material 1 is at least one of the resin having the cyclic structure compound and the cyclic structure in part. In the case of containing these, the etching resistance is remarkably excellent. In this case, even if the resist pattern 3 (inner layer resist pattern 10b) is a material having poor etching resistance, the thickened resist pattern 10 having the surface layer 10a having excellent etching resistance on the surface thereof can be formed.

  The resist pattern manufactured by the resist pattern forming method of the present invention has a surface layer formed by mixing the resist pattern thickening material of the present invention on the surface of the resist pattern. When the resist pattern thickening material contains at least one of the aromatic compound and a resin partially containing the aromatic compound, even if the resist pattern is a material having poor etching resistance, the resist pattern A resist pattern having a surface layer with excellent etching resistance on the surface can be efficiently produced. Further, since the thickened resist pattern manufactured by the resist pattern forming method of the present invention is thickened by the thickness of the surface layer as compared with the resist pattern, the thickened resist pattern 10 manufactured is The width of the resist missing pattern formed by the above is smaller than the width of the resist missing pattern formed by the resist pattern. Therefore, according to the resist pattern forming method of the present invention, a fine resist missing pattern is efficiently formed. can do.

The thickened resist pattern formed of the resist pattern thickening material of the present invention has a surface layer formed of the resist pattern thickening material of the present invention on the resist pattern.
The thickened resist pattern preferably has excellent etching resistance, and the etching rate (Å / s) is preferably equal to or higher than that of the resist pattern. Specifically, the ratio (resist pattern / surface layer) between the etching rate (Å / s) of the surface layer and the etching rate (Å / s) of the resist pattern when measured under the same conditions is 1.1. Preferably, it is 1.2 or more, more preferably 1.3 or more.
The etching rate (Å / s) is measured, for example, by performing a predetermined time etching process using a known etching apparatus, measuring the film thickness of the sample, and calculating the film thickness per unit time. be able to.

The surface layer can be suitably formed using the resist pattern thickening material of the present invention, and from the viewpoint of improving etching resistance, a resin having the cyclic structure compound and the cyclic structure in part. It is preferable to contain at least one of the following.
Whether or not the surface layer contains at least one of the cyclic structure compound and a resin partially having a cyclic structure is confirmed by, for example, analyzing an IR absorption spectrum for the surface layer. be able to.

  The thickened resist pattern may contain at least one of the cyclic structure compound and a resin partially having a cyclic structure. In this case, it may be designed such that the content of at least one of the cyclic structure compound and the resin partially having the cyclic structure gradually decreases from the surface layer toward the inside.

The thickened resist pattern may have a structure where the boundary between the resist pattern and the surface layer is clear or an unclear structure.
The thickened resist pattern manufactured by 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). ), Etc., optical components used for connection of optical wiring, microparts such as microactuators, and semiconductor devices, and can be suitably used for the semiconductor device manufacturing method of the present invention described later. Can be used.

(Method for manufacturing semiconductor device)
The method for manufacturing a semiconductor device of the present invention includes a thickened resist pattern forming step and a patterning step, and further includes other steps appropriately selected as necessary.

In the thickening resist pattern forming step, after forming a resist pattern on the underlayer, the resist pattern thickening material of the present invention is applied so as to cover the surface of the resist pattern, thereby thickening the resist pattern. Forming a thickened resist pattern. Details in the thickening resist pattern forming step are the same as those of the resist pattern forming method of the present invention.
The underlayer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include surface layers of various members in a semiconductor device, and examples include a substrate such as a silicon wafer or a surface layer thereof, various oxidation layers. A film etc. are mentioned suitably. The resist pattern is as described above. The application method is as described above. Further, after the application, it is preferable to perform the above-described pre-baking, baking and the like.

The patterning step is a step of patterning the base layer by performing etching (using as a mask pattern or the like) using the thickened resist pattern formed by the thickened resist pattern forming step.
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.

  As said other process, a surfactant application | coating process, a development processing process, etc. are mentioned suitably, for example.

The surfactant applying step is a step of applying the surfactant to the surface of the resist pattern before the thickening resist pattern forming step.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, those described above are preferably used, and examples include polyoxyethylene-polyoxypropylene condensate compounds, polyoxyalkylene alkyl ethers. Compounds, polyoxyethylene alkyl ether compounds, polyoxyethylene derivative compounds, sorbitan fatty acid ester compounds, glycerin fatty acid ester compounds, primary alcohol ethoxylate compounds, phenol ethoxylate compounds, nonylphenol ethoxylates, octylphenol ethoxylates, lauryl alcohol Ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, secondary alcohol ethoxylate, alcohol Kirukachion system, amide quaternary cationic, ester quaternary cationic, amine oxide, and the like betaine.

  The development processing step is a step of developing the applied resist pattern thickening material after the thickening resist pattern forming step and before the patterning step. The development processing is as described above.

  According to the semiconductor device manufacturing method of the present invention, for example, various semiconductor devices including flash memory, DRAM, FRAM, and the like can be efficiently manufactured.

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

Example 1
-Preparation of resist pattern thickening material-
Resist pattern thickening materials 1 to 4 having the compositions shown in Table 1 were prepared. In Table 1, the unit of numerical values in parentheses represents parts by mass. “KW-3” in the “resin” column represents a polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.). In the “surfactant” column, “TN-80” represents a nonionic surfactant (manufactured by Asahi Denka Co., Ltd., primary alcohol etoxychelate ), and “PC-6” represents a nonionic surfactant. Agent (Asahi Denka Co., Ltd., special phenol ethoxy chelate ). Further, as a main solvent component excluding the resin, a mixed solution of pure water (deionized water) and isopropyl alcohol (mass ratio is pure water (deionized water): isopropyl alcohol = 98.6: 0.4). used.

-Formation of resist pattern-
The resist pattern thickening materials 1 to 4 of the present invention prepared as described above were first applied by spin coating on an isolated line pattern (diameter 200 nm) formed by the ArF resist (manufactured by Sumitomo Chemical Co., Ltd., PAR700). After applying at 1,000 rpm / 5 s, then at 3,500 rpm / 40 s, pre-baking at 85 ° C./70 s, and further baking at 110 ° C./70 s. By rinsing the resist pattern thickening materials 1 to 4 with pure water for 60 seconds, removing the unmixed portion, and developing the resist pattern thickened by the resist pattern thickening materials 1 to 4, A thickened resist pattern was formed.

  The size of the resist omission pattern formed by the formed thickened resist pattern is shown in Table 2 together with the initial pattern size (the size of the resist omission pattern formed by the resist pattern before thickening). In Table 2, “1” to “4” correspond to the resist pattern thickening materials 1 to 4.

Next, the resist pattern thickening materials 1 to 4 of the present invention were applied to the surface of the resist formed on the silicon substrate to form a surface layer having a thickness of 0.5 μm. These surface layers, the KrF resist for comparison (manufactured by Shipley Co., Ltd., UV-6), and polymethyl methacrylate (PMMA) for comparison are etched with an etching apparatus (parallel plate type RIE apparatus, Fujitsu Limited). The product was etched for 3 minutes under the conditions of Pμ = 200 W, pressure = 0.02 Torr, CF ₄ gas = 100 sccm, the amount of film reduction of the sample was measured, the etching rate was calculated, and the KrF resist Relative evaluation was performed based on the etching rate.

  From the results shown in Table 3, in the resist pattern thickening material of the present invention, the resist pattern using adamantanol, which is an alicyclic compound, is close to the KrF resist and has significantly higher etching resistance than the PMMA. It can be seen that the thickening material 2 is particularly excellent in etching resistance.

(Example 2)
As shown in FIG. 3A, an interlayer insulating film 12 was formed on the silicon substrate 11, and as shown in FIG. 3B, a titanium film 13 was formed on the interlayer insulating film 12 by sputtering. Next, as shown in FIG. 3C, a resist pattern 14 is formed by a known photolithography technique, and this is used as a mask, and the titanium film 13 is patterned by reactive ion etching to form an opening 15a. . Subsequently, as shown in FIG. 3D, 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.

Next, the titanium film 13 is removed by wet processing, and as shown in FIG. 4A, 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. A film was formed by electrolytic plating. Next, as shown in FIG. 4B, planarization is performed by leaving the barrier metal and the Cu film (first metal film) only in the groove corresponding to the opening 15b (FIG. 3D) by CMP. A single layer of wiring 17a was formed.
Next, as shown in FIG. 4C, after an interlayer insulating film 18 is formed on the first layer wiring 17a, FIGS. 3B to 3D, FIGS. 4A and 4B, Similarly, as shown in FIG. 4D, a Cu plug (second metal film) 19 and a TiN film 16a that connect the first layer wiring 17a 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. 5, the illustration of the barrier metal layer formed below the wiring of each layer is omitted.
In Example 2, the resist pattern 14 is a thickened resist pattern manufactured in the same manner as in Example 1 using the resist pattern thickening material of the present invention.

(Example 3)
-Flash memory and its manufacture-
Example 3 is an example of a semiconductor device of the present invention using the resist pattern thickening material of the present invention and a manufacturing method thereof. In this Example 3, the following resist films 26, 27, 29, 32 and 34 are thickened by the same method as in Examples 1 and 2 using the resist pattern thickening material of the present invention. It has been done.

  (A) and (b) in FIG. 6 are top views (plan views) of a FLASH EPROM called a FLOTOX type or an ETOX type, and (a) to (c) in FIG. 7 and (d) to (d) in FIG. FIGS. 9 (g) to 9 (i) are cross-sectional schematic views for explaining an example of the manufacturing method of the FLASH EPROM. FIGS. 7 to 9 show the memory cell portion (first element). FIG. 6 is a schematic cross-sectional view (A-direction cross-section) in the gate width direction (X direction in FIG. 6) of a portion where a MOS transistor having a floating gate electrode is formed. FIG. 6 is a schematic cross-sectional view (B-direction cross-section) of the memory cell portion in the gate length direction (Y direction in FIG. 6) orthogonal to the X direction, and the right figure shows the MOS in the peripheral circuit portion (second element region). Transistor shape It is the cross section (A direction cross section in FIG. 6) schematic of the part formed.

First, as shown in FIG. 7A, 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. 7A), the peripheral circuit portion ( The right side of FIG. 7A was masked with the 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 of FIG. 7B), a memory cell portion (FIG. The left figure and the middle figure of FIG. 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 a floating gate electrode of the MOS transistor in the memory cell portion (the left diagram and the central diagram in FIG. 7C) and a gate electrode of the MOS transistor in the peripheral circuit portion (the right diagram in FIG. 7C) A first polysilicon film (first conductor film) 28 having a thickness of 500 to 2,000 mm (50 to 200 nm) was formed on the entire surface.

  Thereafter, as shown in FIG. 8D, the first polysilicon film 28 is patterned with a resist film 29 formed as a mask, and the MOS transistor of the memory cell portion (the left and center views of FIG. 8D) is formed. The floating gate electrode 28a was formed. At this time, as shown in FIG. 8D, patterning is performed so that the X dimension has a final dimension width, and the Y direction is not patterned, and the region that becomes the S / D region layer is covered with a resist film 29. I left it.

Next, as shown in the left diagram and the central diagram in FIG. 8E, after removing the resist film 29, the capacitor insulating film 30a made of SiO ₂ film is formed so as to cover the floating gate electrode 28a. It was formed by thermal oxidation so that the thickness was about 200 to 500 mm (20 to 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. 8E). 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. 8E, the thickness of the second polysilicon film (second conductor film) 31 to be the control gate electrode is set so as to cover the floating gate electrode 28a and the capacitor insulating film 30a. It formed so that it might become 500-2,000 mm (50-200 nm).

  Next, as shown in FIG. 8 (f), the memory cell portion (the left and center views of FIG. 8 (f)) is masked with a resist film 32, and the peripheral circuit portion (the right side of FIG. 8 (f)) is masked. The second polysilicon film 31 and the capacitor insulating film 30b in the figure were sequentially removed by etching, and the first polysilicon film 28 was exposed.

  Next, as shown in FIG. 9G, the second polysilicon film 31, the capacitor insulating film 30a, and the X direction of the memory cell portion (the left diagram and the central diagram in FIG. 9G) are patterned. Using the resist film 32 as a mask, the first polysilicon film 28a is patterned in the Y direction so as to have the final dimensions of the first gate portion 33a, and the control gate electrode 31a / capacitor having a width of about 1 μm in the Y direction. A stack of insulating film 30c / floating gate electrode 28c is formed, and a second gate portion is formed on resist film 32 as a mask with respect to first polysilicon film 28 in the peripheral circuit portion (the right diagram in FIG. 9G). Patterning was performed to obtain a final dimension of 33b to form a gate electrode 28b having a width of about 1 μm.

Next, using the stack of the control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c in the memory cell portion (the left and center views of FIG. 9H) as a mask, the silicon substrate 22 in the element formation region is dosed. An amount of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² of phosphorus (P) or arsenic (As) is introduced by ion implantation to form n-type S / D region layers 35a and 35b, and the peripheral circuit Using the gate electrode 28b of the portion (right of FIG. 8H) as a mask, phosphorus (P) with a dose of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² as an n-type impurity in the Si substrate 22 in the element formation region Alternatively, arsenic (As) was introduced by ion implantation to form S / D region layers 36a and 36b.

Next, the first gate portion 33a of the memory cell portion (the left view and the center view of FIG. 9 (i)) and the second gate portion 33b of the peripheral circuit portion (the right view of FIG. 9 (i)) are connected to the PSG. An interlayer insulating film 37 made of a 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. 9I, a FLASH EPROM was manufactured as a semiconductor device.

In this FLASH EPROM, the second gate insulating film 24b of the peripheral circuit portion (the right diagram in FIGS. 7A to 9F) is formed from the first polysilicon film 28 or the gate electrode 28b from the beginning to the end. Since it is covered (the right figure in FIG. 8C to FIG. 9F), the second gate insulating film 24b keeps 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 FIG. 6) and then patterning in the gate length direction (Y direction in FIG. 6). However, the pattern is patterned with a predetermined width in the gate length direction (Y direction in FIG. 6) and then patterned in the gate width direction (X direction in FIG. 6). It is good.

The manufacturing examples of FLASH EPROM shown in FIGS. 10A to 10C are the same as those shown in FIGS. 10A to 10C except that the steps shown in FIG. Is the same as in the above embodiment. That is, as shown in FIG. 10A, the second polysilicon film 31 and the peripheral circuit portion (the right view of FIG. 10A) of the memory cell portion (the left view and the center view in FIG. 10A). ) On the first polysilicon film 28, a refractory metal film (fourth conductor film) 42 made of a tungsten (W) film or a titanium (Ti) film is made to have a thickness of about 2,000 mm (200 nm). This embodiment differs from the above embodiment only in that a polycide film is provided. The steps after FIG. 10A, that is, the steps shown in FIGS. 10B to 10C were performed in the same manner as FIGS. 9G to 9I. The description of the same steps as those in FIGS. 9G to 9I is omitted, and in FIGS. 10A to 10C, the same steps as those in FIGS. 9G to 9I are denoted by the same symbols.
As a result, as shown in FIG. 10C, 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 manufacturing example of the FLASH EPROM shown in FIGS. 11A to 11C 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. 11A). Similarly to the first gate portion 33a of the memory cell portion (first element region) (left and center views in FIG. 11A), the first polysilicon film 28b (first conductor film) / SiO _{2 is formed.} A structure of film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is formed, and as shown in FIG. 11B or 11C, the first polysilicon film 28b and the second polysilicon film are formed. This embodiment is the same as the above embodiment except that the gate electrode is formed by short-circuiting the film 31b.

Here, as shown in FIG. 11B, the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film). An opening 52a penetrating through the second gate portion 33c shown in FIG. 11A, for example, is formed on an insulating film 54, for example, and a third conductor film such as a W film is formed in the opening 52a. Alternatively, the first polysilicon film 28b and the second polysilicon film 31b are short-circuited by embedding a refractory metal film 53a such as a Ti film. Further, as shown in FIG. 11C, an opening 52b penetrating the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) is formed, and the bottom of the opening 52b is formed. After exposing the first polysilicon film 28b as the lower layer, 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, thereby forming the first polysilicon film. 28b and the second polysilicon film 31b are short-circuited.

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

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

12A to 12D are process diagrams for explaining the manufacture of the magnetic head.
First, as shown in FIG. 12 (A), a resist film is formed on the interlayer insulating layer 100 so as to have a thickness of 6 μm, and exposure and development are performed to form an opening pattern for forming a spiral thin film magnetic coil. A resist pattern 102 having the following was formed.
Next, as shown in FIG. 12B, a thickness of 0.01 μm is formed 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 base layer 106 formed by laminating a Ti adhesion film and a Cu adhesion film having a thickness of 0.05 μm was formed by vapor deposition.
Next, as shown in FIG. 12C, a portion of the interlayer insulating layer 100 where the resist pattern 102 is not formed, that is, the surface of the plating base layer 106 formed on the exposed surface of the opening 104 is formed. A thin film conductor 108 made of a Cu plating film having a thickness of 3 μm was formed.
Next, as shown in FIG. 12D, when the resist pattern 102 is dissolved and removed and lifted off from 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 thickened using the resist pattern thickening material of the present invention, the thin film magnetic coil 110 is fine and fine. In addition, it is excellent in mass productivity.

13 to 18 are process diagrams for explaining the manufacture of another magnetic head.
As shown in FIG. 13, a gap layer 114 was formed on a nonmagnetic substrate 112 made of ceramic by a sputtering method. Although not shown, an insulating layer made of silicon oxide and a conductive underlayer made of Ni—Fe permalloy are previously formed on the nonmagnetic substrate 112 by sputtering, and the lower magnetic layer made of Ni—Fe permalloy is formed. A 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. 14, the resist film 118 was exposed and developed to form a spiral pattern. Then, as shown in FIG. 15, the resist film 118 having the spiral pattern was subjected to a thermosetting process at several hundred degrees C. for about one hour to form a first spiral pattern 120 having a protrusion shape. Further, a conductive base layer 122 made of Cu was formed on the surface.

Next, as shown in FIG. 16, a resist material is applied onto the conductive base layer 122 by spin coating to form a resist film 124, and then the resist film 124 is patterned on the first spiral pattern 120. A resist pattern 126 was formed.
Next, as shown in FIG. 17, a Cu conductor layer 128 was formed by plating on the exposed surface of the conductive base layer 122, that is, on the portion where the resist pattern 126 was not formed. Thereafter, as shown in FIG. 18, the resist pattern 126 was dissolved and removed to lift off the conductive base layer 122, and a spiral thin film magnetic coil 130 formed of the Cu conductor layer 128 was formed.
As described above, as shown in the plan view of FIG. 19, a magnetic head having the magnetic layer 132 on the resin insulating film 116 and the thin film magnetic coil 130 provided on the surface was manufactured.

  In the magnetic head obtained here, the spiral pattern is finely formed by the resist pattern 126 thickened using the resist pattern thickening material of the present invention, so that the thin film magnetic coil 130 is fine and fine. In addition, it is excellent in mass productivity.

Here, it will be as follows if the preferable aspect of this invention is appended.
(Additional remark 1) Resist pattern thickening material characterized by containing resin and surfactant.
(Supplementary note 2) The resist pattern thickening material according to supplementary note 1, which is water-soluble or alkali-soluble.
(Appendix 3) The resist according to appendix 1 or 2, wherein the surfactant is at least one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Pattern thickening material.
(Supplementary Note 4) The nonionic surfactant is a polyoxyethylene-polyoxypropylene condensate compound, polyoxyalkylene alkyl ether compound, polyoxyethylene alkyl ether compound, polyoxyethylene derivative compound, sorbitan fatty acid ester compound, glycerin fatty acid. Select from ester compounds, primary alcohol ethoxylate compounds, phenol ethoxylate compounds, alkoxylate surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, and ethylenediamine surfactants And
The cationic surfactant is selected from alkyl cationic surfactants, amide type quaternary cationic surfactants, and ester type quaternary cationic surfactants;
4. The resist pattern thickening material according to supplementary note 3, wherein the amphoteric surfactant is selected from an amine oxide surfactant and a betaine surfactant.
(Supplementary note 5) The resist pattern thickening material according to any one of supplementary notes 1 to 4, wherein the resin is at least one of water-soluble and alkali-soluble.
(Supplementary note 6) The resist pattern thickening material according to any one of supplementary notes 1 to 5, wherein the resin is at least one selected from polyvinyl alcohol, polyvinyl acetal, and polyvinyl acetate.
(Supplementary note 7) The resist pattern thickening material according to any one of supplementary notes 1 to 6, wherein the resin has a cyclic structure at least in part.
(Supplementary note 8) The resist pattern thickening material according to supplementary note 7, wherein the cyclic structure is a structure selected from at least one of an aromatic compound, an alicyclic compound, and a heterocyclic compound.
(Supplementary note 9) The resist pattern thickening material according to any one of supplementary notes 1 to 8, which contains a cyclic structure compound.
(Supplementary note 10) The resist pattern thickening material according to supplementary note 9, wherein the cyclic structure compound is at least one of water-soluble and alkali-soluble.
(Appendix 11) The resist pattern thickening material according to appendix 9 or 10, wherein the cyclic structure compound is selected from at least one of an aromatic compound, an alicyclic compound, and a heterocyclic compound.
(Supplementary note 12) The aromatic compound is selected from a polyphenol compound, an aromatic carboxylic acid compound, a naphthalene polyhydric alcohol compound, a benzophenone compound, a flavonoid compound, a derivative thereof and a glycoside thereof,
The resist pattern thickening material according to appendix 11, wherein the alicyclic compound is selected from polycycloalkanes, cycloalkanes, steroids, derivatives thereof, and glycosides thereof.
(Additional remark 13) The resist pattern thickening material in any one of Additional remark 1 to 12 containing an organic solvent.
(Supplementary note 14) In Supplementary note 13, the organic solvent is at least one selected from alcohol solvents, chain ester solvents, cyclic ester solvents, ketone solvents, chain ether solvents, and cyclic ether solvents. The resist pattern thickening material described.
(Additional remark 15) The resist pattern characterized by apply | coating the resist pattern thickening material in any one of Additional remark 1 to 14 so that the surface of this resist pattern may be covered after forming a resist pattern.
(Appendix 16) After forming the resist pattern, the resist pattern thickening material according to any one of appendices 1 to 15 is applied so as to cover the surface of the resist pattern, and the resist pattern is thickened. A method for forming a resist pattern, comprising forming a resist pattern.
(Supplementary note 17) The resist pattern forming method according to supplementary note 16, wherein after the resist pattern thickening material is applied, the resist pattern thickening material is developed.
(Additional remark 18) The semiconductor device characterized by having the pattern formed using the resist pattern thickened with the resist pattern thickening material in any one of Additional remark 1 to 14.
(Appendix 19) After forming a resist pattern on the underlayer, the resist pattern thickening material according to any one of appendices 1 to 14 is applied so as to cover the surface of the resist pattern, and the resist pattern is thickened. A method of manufacturing a semiconductor device, comprising: a thickened resist pattern forming step of forming a thickened resist pattern; and a patterning step of patterning the underlayer by etching using the thickened resist pattern .
(Supplementary Note 20) At least the material of the resist pattern is selected from a novolak resist, a PHS resist, an acrylic resist, a cycloolefin-maleic anhydride resist, a cycloolefin resist, and a cycloolefin-acryl hybrid resist 20. The method for manufacturing a semiconductor device according to appendix 19, which is one type.

The resist pattern thickening material of the present invention thickens a resist pattern made of ArF resist or the like, and uses light at the time of patterning exposure, while exceeding the light exposure limit, a pattern such as a resist omission pattern or a wiring pattern The resist pattern thickening material of the present invention can be suitably applied to various patterning methods, semiconductor manufacturing methods, and the like. And the method for manufacturing a semiconductor device of the present invention can be used particularly preferably.
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, fine components such as microactuators, and semiconductor devices, and can be preferably used in the method of manufacturing a semiconductor device of the present invention.
The semiconductor device manufacturing method of the present invention can be suitably used for manufacturing various semiconductor devices including flash memory, DRAM, FRAM, and the like.

FIG. 1 is a schematic diagram for explaining the mechanism of thickening a resist pattern using the resist pattern thickening material of the present invention. FIG. 2 is a schematic view for explaining an example of a resist pattern forming method of the present invention. FIG. 3 is a schematic diagram for explaining an example of a process for manufacturing a semiconductor device having a multilayer wiring structure by the method for manufacturing a semiconductor device of the present invention (part 1). FIG. 4 is a schematic diagram for explaining an example of a process for manufacturing a semiconductor device having a multilayer wiring structure by the method for manufacturing a semiconductor device of the present invention (part 2). FIG. 5 is a schematic diagram for explaining an example of a process for manufacturing a semiconductor device having a multilayer wiring structure by the method for manufacturing a semiconductor device of the present invention (part 3). FIG. 6 is a top view for explaining a FLASH EPROM which is an example of the semiconductor device of the present invention. FIG. 7 is a schematic cross-sectional view (No. 1) for explaining the manufacturing method of the FLASH EPROM as an example relating to the manufacturing method of the semiconductor device of the present invention. FIG. 8 is a schematic cross-sectional view (No. 2) for explaining the manufacturing method of the FLASH EPROM which is an example relating to the manufacturing method of the semiconductor device of the present invention. FIG. 9 is a schematic cross-sectional view (No. 3) for explaining the manufacturing method of the FLASH EPROM which is an example relating to the manufacturing method of the semiconductor device of the present invention. FIG. 10 is a schematic cross-sectional view for explaining a manufacturing method of FLASH EPROM which is another example of the manufacturing method of the semiconductor device of the present invention. FIG. 11 is a schematic cross-sectional view for explaining a method for manufacturing a FLASH EPROM, which is another example of the method for manufacturing a semiconductor device of the present invention. FIG. 12 is a schematic cross-sectional view for explaining an example in which a resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 13 is a schematic cross-sectional view for explaining another example process (part 1) in which a resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 14 is a schematic cross-sectional view for explaining another example process (part 2) in which the resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 15 is a schematic cross-sectional view for explaining another example process (No. 3) in which a resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 16 is a schematic cross-sectional view for explaining another example process (part 4) in which the resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 17 is a schematic cross-sectional view for explaining another example process (No. 5) in which a resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 18 is a schematic cross-sectional view for explaining another example process (No. 6) in which a resist pattern thickened using the resist pattern thickening material of the present invention is applied to the manufacture of a magnetic head. FIG. 19 is a plan view showing an example of the magnetic head manufactured in the steps of FIGS.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resist pattern thickening material 3 Resist pattern 3a Resist material 5 Underlayer (base material)
DESCRIPTION OF SYMBOLS 10 Thickening resist pattern 10a Surface layer 10b Resist pattern 11 Silicon substrate 12 Interlayer insulating film 13 Titanium film 14 Resist pattern 15a Opening 15b Opening 16 TiN film 17 Cu film 17a First layer wiring 18 Interlayer insulating film 19 Cu plug 20 Second layer wiring 21 Third layer 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 portion 33b second gate portion 33c second gate portion 34 resist film 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 Plating underlayer 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 ground layer 124 Resist film 126 Resist pattern 128 Cu conductor layer 130 Thin film magnetic coil 132 Magnetic layer

Claims (6)

After forming a resist pattern by ArF resist, so as to cover the surface of the resist pattern formed by the ArF resist, and a resin, the resist pattern thickening material containing a primary alcohol ethoxylate Kishireto coated, the resist A method of forming a resist pattern, comprising forming a thickened resist pattern having a thickened pattern.   The method for forming a resist pattern according to claim 1, wherein the resist pattern thickening material further contains adamantanol.   The method for forming a resist pattern according to claim 1, wherein after the application of the resist pattern thickening material, development processing of the resist pattern thickening material is performed. After forming a resist pattern by ArF resist on an underlying layer so as to cover the surface of the resist pattern formed by the ArF resist, and a resin, the resist pattern thickening material containing a primary alcohol ethoxylate Kishireto coating And a thickening resist pattern forming step for forming a thickening resist pattern obtained by thickening the resist pattern, and a patterning step for patterning the underlayer by etching using the thickening resist pattern. A method of manufacturing a semiconductor device.   The method for manufacturing a semiconductor device according to claim 4, wherein the resist pattern thickening material further contains adamantanol. After forming a resist pattern by ArF resist on an underlying layer so as to cover the surface of the resist pattern formed by the ArF resist, and a resin, the resist pattern thickening material containing a primary alcohol ethoxylate Kishireto coating And a thickening resist pattern forming step for forming a thickening resist pattern obtained by thickening the resist pattern, and a patterning step for patterning the underlayer by etching using the thickening resist pattern. A method of manufacturing a magnetic head.