Resist pattern, method for manufacturing the same, and semiconductor device and method for manufacturing the same

The present invention relates to a fine resist pattern obtained by thinning the resist pattern at the time of patterning and an efficient method for producing the resist pattern, and a semiconductor device obtained by using the pattern based on the resist pattern and the efficient semiconductor device. Regarding the manufacturing method.

Recently, semiconductor integrated circuits have become highly integrated, and LSIs and VLSIs have been put into practical use. Along with this, the development of technology for miniaturizing wiring patterns is being promoted. Conventionally, a lithography technique has been used to form the wiring pattern. In the case of this lithography technique, for example, a substrate to be processed on which a thin film is formed is coated with a resist film, selective exposure is performed, and then development is performed. To form a resist pattern, dry etching is performed using this as a mask, and then the resist pattern is removed to obtain a desired wiring pattern.

By the way, in order to miniaturize the wiring pattern, it is necessary to both shorten the wavelength of the exposure light source and develop a resist material having a high resolution according to the characteristics of the light source. However, in order to shorten the wavelength of the light source, it is necessary to further improve the existing exposure apparatus, which requires a huge cost. On the other hand, the demand for continuing to use light exposure mainly for maintaining high mass productivity is still strong even now that the wiring pattern is miniaturized. On the other hand, there is a problem that it is not easy to develop a resist material having a high resolution.

<p> An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, an object of the present invention is to provide a method for producing a resist pattern, which can use light as exposure light, is excellent in mass productivity, and can produce a fine resist pattern finely beyond the exposure limit of light. Another object of the present invention is to provide a fine resist pattern obtained by thinning the resist pattern. Another object of the present invention is to provide a high-performance semiconductor device obtained by using a fine resist pattern. Further, the present invention is a semiconductor device that can use light as exposure light, has excellent mass productivity, and can efficiently mass-produce a semiconductor device obtained by using a fine resist pattern formed finely beyond the exposure limit of light. It is an object of the present invention to provide the manufacturing method of.</p>

<p> The means for solving the above-mentioned problems are as described later as (Appendix 1) to (Appendix 22). When the resist pattern thinning material according to (Appendix 1) is applied onto the resist pattern, among the resist pattern thinning materials, those near the interface with the resist pattern permeate into the resist pattern. A mixing layer is formed on the surface of the resist pattern. After that, the resist pattern thinning material and the mixing layer are removed, and the resist pattern obtained is thinned by the amount from which the mixing layer is removed, and has a fine structure. The resist pattern thinning material described in (Appendix 2) to (Appendix 3) exhibits sufficient water developability. The resist pattern thinning material described in (Appendix 4) to (Appendix 5) can be used as an aqueous coating solution because the water-soluble resin exhibits sufficient water solubility. The resist pattern thinning material described in (Appendix 6) to (Appendix 7) exhibits sufficient alkali developability. The resist pattern thinning material described in (Appendix 8) to (Appendix 10) can be used as an aqueous coating solution because the alkali-soluble resin exhibits sufficient alkali solubility.</p><p> The resist pattern thinning material described in (Appendix 11) to (Appendix 12) contains a cross-linking agent, and the resist pattern thinning material described in (Appendix 13) to (Appendix 14) contains a surfactant. Since it is contained, it has a high affinity with the resist pattern, and when it is applied onto the resist pattern, the resist pattern is thinned. Since the resist pattern thinning material according to (Appendix 15) to (Appendix 16) contains a solvent, it is highly soluble in the water-soluble resin, the alkali-soluble resin, and the like, and is applied onto the resist pattern. Then, the resist pattern is thinned.</p><p> In the method for producing a resist pattern according to (Appendix 17), after the resist pattern is formed, the resist pattern thinning material is applied onto the resist pattern. Then, the resist pattern thinning material near the interface with the resist pattern soaks into the resist pattern, and a mixing layer of the resist pattern material and the resist pattern thinning material is formed on the surface of the resist pattern. To. After that, the resist pattern thinning material and the mixing layer are removed, and the resist pattern obtained is thinned by the amount from which the mixing layer is removed, and has a fine structure. In the method for producing a resist pattern according to (Appendix 18) to (Appendix 19), since the resist pattern thinning material is applied and then developed, the mixing layer is surely dissolved and removed, and the resist pattern is formed. It will be thinned.</p><p> The resist pattern described in (Appendix 20) has a fine structure because it is obtained by the method for producing the resist pattern. Since the semiconductor device according to (Appendix 21) is obtained by using the resist pattern, it has high quality and high performance. In the method for manufacturing a semiconductor device according to (Appendix 22), after a resist pattern is formed on the base layer, the resist pattern thinning material is applied onto the resist pattern. Then, the resist pattern thinning material near the interface with the resist pattern soaks into the resist pattern, and a mixing layer of the resist pattern material and the resist pattern thinning material is formed on the surface of the resist pattern. To. After that, the resist pattern thinning material and the mixing layer are removed, and the resist pattern obtained is thinned by the amount from which the mixing layer is removed, and has a fine structure. Then, since the base layer is patterned by etching using the resist pattern as a mask, a high-quality and high-performance semiconductor device can be efficiently manufactured.</p>

<p> According to the present invention, the conventional problems can be solved. That is, the present invention can provide a method for producing a resist pattern, which can use light as exposure light, is excellent in mass productivity, and can finely produce a fine resist pattern beyond the exposure limit of light. Further, the present invention can provide a fine resist pattern obtained by thinning the resist pattern. Further, the present invention can provide a high-performance semiconductor device obtained by using a fine resist pattern. Further, the present invention is a semiconductor device that can use light as exposure light, has excellent mass productivity, and can efficiently mass-produce a semiconductor device obtained by using a fine resist pattern formed finely beyond the exposure limit of light. Manufacturing method can be provided.</p>

(Resist pattern thinning material) The resist pattern thinning material in the present invention contains at least one selected from a water-soluble resin and an alkali-soluble resin, and further contains a cross-linking agent, a surfactant, and a solvent, if necessary. , Contains other ingredients. The mode of the resist pattern thinning material in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but may be an aqueous solution, a colloidal liquid, an emulsion, or the like. , It is preferably in the form of an aqueous solution.

-Water-soluble resin-The water-soluble resin is not particularly limited as long as it is water-soluble and can be appropriately selected depending on the intended purpose, but it dissolves in an amount of 0.1 g or more in 100 g of water at 25 ° C. Those showing water solubility are preferable.

The water-soluble resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyacrylic acid, polyvinylpyrrolidone, polyethyleneimine, polyethylene oxide, styrene- Examples thereof include maleic acid copolymers, polyvinylamines, polyallylamines, oxazoline group-containing water-soluble resins, water-soluble melamine resins, water-soluble urea resins, alkyd resins, and sulfonamide resins. These water-soluble resins may be used alone, in combination of two or more, or in combination with the alkali-soluble resin.

The content of the water-soluble resin in the resist pattern thinning material varies depending on the type, content, etc. of the cross-linking agent, the surfactant, the solvent, etc., and cannot be unconditionally defined, but it depends on the purpose. It can be decided as appropriate.

-Alkali-soluble resin-The alkali-soluble resin is not particularly limited as long as it is soluble in alkali and can be appropriately selected depending on the intended purpose. However, 2.38% tetramethylammonium hydro at 25 ° C. Those exhibiting alkali solubility, which dissolves 0.1 g or more in 100 g of an aqueous oxide (TMAH) solution, are preferable.

The alkali-soluble resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, itaconic acid, vinylbenzoic acid, vinylphenol, styrene, polyhydric phenol, and polyvalent. Examples thereof include those having at least one selected from alcohols and derivatives thereof as a monomer unit. Specific examples of the alkali-soluble resin include novolak resin, vinylphenol resin, polyacrylic acid, polymethacrylic acid, polyp-hydroxyphenylacryllate, polyp-hydroxyphenylmethacrylate, and copolymer resins thereof. Preferred. These alkali-soluble resins may be used alone, in combination of two or more, or in combination with the water-soluble resin.

The content of the alkali-soluble resin in the resist pattern thinning material varies depending on the type, content, etc. of the cross-linking agent, the surfactant, the solvent, etc., and cannot be unconditionally defined, but it depends on the purpose. It can be decided as appropriate.

-Crosslinking agent-The cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, water-soluble ones that cause cross-linking by heat or acid are preferable, for example, amino-based cross-linking agents and melamine derivatives. , Urea-based derivatives, and the like are preferable. These may be used alone or in combination of two or more. Examples of the amino-based cross-linking agent include benzoguanamine and derivatives thereof. Examples of the melamine derivative include alkoxymethylmelamine and derivatives thereof. Examples of the urea-based derivative include urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea, ethylene urea carboxylic acid, glycol uryl, and derivatives thereof.

The content of the cross-linking agent in the resist pattern thinning material varies depending on the type, content, etc. of the water-soluble resin, the alkali-soluble resin, the surfactant, the solvent, and the like, and cannot be unconditionally defined. , Can be appropriately determined according to the purpose.

-Surfactant- The surfactant can be suitably used when the affinity between the resist pattern thinning material and the resist pattern to which the resist pattern thinning material is applied is not sufficient, and the surfactant can be used. Is contained in the resist pattern thinning material, the mixing layer can be efficiently formed on the surface of the resist pattern, the resist pattern can be thinned and made finer, and the resist pattern can be made finer. It is possible to effectively suppress the foaming of the thinning material.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a silicone-based surfactant. Examples thereof include agents, but nonionic surfactants are preferable in terms of a structure that does not contain metal ions. These may be used alone or in combination of two or more.

Specific examples of the surfactant include polyoxyethylene-polyoxypropylene condensate surfactant, polyoxyalkylene alkyl ether surfactant, polyoxyethylene alkyl ether surfactant, and polyoxyethylene derivative surfactant. Examples thereof include activators, sorbitan fatty acid ester-based surfactants, glycerin fatty acid ester-based surfactants, primary alcohol ethoxylate-based surfactants, and phenol ethoxylate-based surfactants.

The content of the surfactant in the resist pattern thinning material varies depending on the type, content, etc. of the water-soluble resin, the alkali-soluble resin, the cross-linking agent, the solvent, and the like, and cannot be unconditionally defined. , Can be appropriately determined according to the purpose.

-Solvent- The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water, alcohol-based solvent and glycol-based solvent.

Examples of the alcohol solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Examples of the glycol-based solvent include ethylene glycol, propylene glycol, propylene glycol methyl ether, dipropylene glycol dimethyl ether, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the resist pattern thinning material varies depending on the type and content of the water-soluble resin, the alkali-soluble resin, the cross-linking agent, the surfactant and the like, and cannot be unconditionally defined. , Can be appropriately determined according to the purpose.

-Other components- 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 depending on the intended purpose. Various known additives such as thermoacid generators and amines can be selected as appropriate. Examples thereof include a system, an amide system, and a quencher typified by ammonium chlorine. The content of the other components in the resist pattern thinning material varies depending on the type, content, etc. of the water-soluble resin, the alkali-soluble resin, the cross-linking agent, the surfactant, the solvent, and the like, and is generally defined. However, it can be appropriately determined according to the purpose.

-Use, etc.-The resist pattern thinning material of the present invention can be applied and used on the resist pattern. At the time of the coating, the surfactant may be separately applied before the resist pattern thinning material is applied without being contained in the resist pattern thinning material.

When the resist pattern thinning material is applied onto the resist pattern, a mixing layer of the resist pattern material and the resist pattern thinning material is formed on the surface of the resist pattern. Then, when the resist pattern thinning material and the mixing layer are removed, a fine resist pattern thinned by the amount from which the mixing layer is removed is formed. In the case where the resist pattern thinning material contains a water-soluble resin, the dissolution rate of the coating film of the resist pattern thinning material in water at 25 ° C. is 10 Å / s or more. Is preferable, and 50 to 1000 Å / s is more preferable. Further, in the case where the resist pattern thinning material contains an alkali-soluble resin, the dissolution rate of the coating film of the resist pattern thinning material in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. It is preferably 10 Å / s or more, and more preferably 50 to 1000 Å / s.

-Material of resist pattern- The material of the resist pattern is not particularly limited and may be appropriately selected from known resist materials according to the purpose, and may be either a negative type or a positive type.

The method, size, thickness, etc. of the resist pattern 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 0.3 to 0.7 μm.

The thinning of the resist pattern using the resist pattern thinning material of the present invention will be described below with reference to the drawings. As shown in FIG. 1 (i), after forming the resist film 2 on the base layer (semiconductor substrate 1), the resist film 2 is exposed and patterned, and as shown in FIG. 1 (ii), the resist pattern 2a Was formed. Examples of the exposure light used for the exposure include g-line, i-line, KrF excimer laser, ArF excimer laser, F2 excimer laser, charged particle beam, and the like, and a known exposure device is used as the exposure method. Can be done. Then, as shown in FIG. 1 (iii), the resist pattern thinning material 3 (pattern reduction material) is applied to the surface of the resist pattern 2a and prebaked (heated / dried) to form a coating film. Then, as shown in FIG. 1 (iv), mixing (impregnation) of the resist pattern thinning material 3 into the resist pattern 2a occurs at the interface between the resist pattern 2a and the resist pattern thinning material 3, and the surface of the resist pattern 2a The mixing layer 4 is formed in. Here, baking may be performed at a temperature higher than the pre-baking (heating / drying). After that, as shown in FIG. 1 (v), the applied resist pattern thinning material 3 and the mixing layer 4 in the resist pattern 2a are formed by developing, that is, a portion having high water solubility or alkali solubility. , A fine resist pattern 2b (reduced resist pattern) that has been dissolved and removed and thinned is formed (developed). The dissolution rate when the mixing layer 4 is dissolved and removed depends on the water solubility or alkali solubility of the resist pattern thinning material 3. Further, the development treatment may be water development or development with a weak alkaline aqueous solution.

-Application-The resist pattern thinning material in the present invention can be more preferably used for thinning the resist pattern, and is particularly suitable for the resist pattern of the present invention and its manufacturing method, and the semiconductor device of the present invention and its manufacturing method. Can be used for.

(Resist pattern and method for producing a resist pattern) The resist pattern of the present invention can be produced by the method for producing a resist pattern of the present invention. In the method for producing a resist pattern of the present invention, after forming the resist pattern, the resist pattern thinning material of the present invention is applied so as to cover the surface of the resist pattern, and the material of the resist pattern is applied to the surface of the resist pattern. At least, it includes forming a mixing layer with the resist pattern thinning material, and further includes performing an appropriately selected treatment such as a developing treatment.

As the material of the resist pattern, those mentioned above in the resist pattern thinning material of the present invention are preferably mentioned. The resist pattern can be formed, for example, according to a known method of patterning a resist film formed on a base (base material). The base material (base material) is not particularly limited and may be appropriately selected depending on the intended purpose. However, when the resist pattern is formed on a semiconductor device, the base material (base material) is a silicon wafer. Etc. is a substrate.

The method for applying the resist pattern thinning material is not particularly limited and may be appropriately selected from known coating methods depending on the intended purpose. For example, a spin coating method is preferable. In the case of the spin coating method, the conditions are, for example, a rotation speed of about 100 to 10000 rpm, preferably 800 to 5000 rpm, a time of about 1 second to 10 minutes, and preferably 1 second to 60 seconds. At the time of the coating, the surfactant may be separately applied before the resist pattern thinning material is applied without being contained in the resist pattern thinning material.

At the interface between the resist pattern and the resist pattern thinning material, the resist pattern thinning material is prebaked (heated and dried) during or after the coating. It is preferable in that mixing (impregnation) of the resist pattern can be efficiently generated. The prebaking (heating / drying) conditions, methods, etc. are not particularly limited and may be appropriately selected depending on the purpose. For example, the temperature is about 40 to 150 ° C, and 70. ~ 120 ° C is preferable, the time is about 10 seconds to 5 minutes, and 30 seconds to 120 seconds is preferable.

Further, after the pre-baking (heating / drying), the applied resist pattern thinning material may be baked. The bake conditions, methods, and the like are not particularly limited and may be appropriately selected depending on the intended purpose, but usually higher temperature conditions than the pre-bake (heating / drying) are adopted. As the baking conditions, for example, the temperature is about 70 to 160 ° C, preferably 90 to 130 ° C, the time is about 10 seconds to 5 minutes, and 30 seconds to 120 seconds is preferable.

Further, after the baking, it is preferable to perform a developing treatment on the applied resist pattern thinning material. When the development treatment is performed, the applied resist pattern thinning material and the mixing layer, that is, the portion having high water solubility or alkali solubility is efficiently dissolved and removed, and a thin resist pattern can be obtained. It is preferable in that respect. The development process is as described above.

Here, the method for producing the resist pattern of the present invention will be described below with reference to the drawings. As shown in FIG. 1 (i), after forming the resist film 2 on the base layer (semiconductor substrate 1), the resist film 2 is patterned to form the resist pattern 2a as shown in FIG. 1 (ii). did. Then, as shown in FIG. 1 (iii), the resist pattern thinning material 3 (pattern reduction material) is applied to the surface of the resist pattern 2a and prebaked (heated / dried) to form a coating film. Then, as shown in FIG. 1 (iv), mixing (impregnation) of the resist pattern thinning material 3 into the resist pattern 2a occurs at the interface between the resist pattern 2a and the resist pattern thinning material 3, and the surface of the resist pattern 2a The mixing layer 4 is formed in. Here, baking may be performed at a temperature higher than the pre-baking (heating / drying). After that, as shown in FIG. 1 (v), by performing a developing process, the applied resist pattern thinning material 3 and the mixing layer 4 in the resist pattern 2a, that is, the highly water-soluble portion, are dissolved and removed. Then, a thin resist pattern 2b (reduced resist pattern) is formed (developed). The development process may be water development or alkali development with a weak alkaline aqueous solution.

The resist pattern of the present invention produced by the method for producing a resist pattern of the present invention has a fine structure because it is thinned by the amount from which the mixing layer is removed. According to the method for producing a resist pattern of the present invention, a fine resist pattern can be efficiently produced.

(Semiconductor Device and Method for Manufacturing Semiconductor Device) The semiconductor device of the present invention is not particularly limited except that it has the resist pattern of the present invention, and known members and the like appropriately selected according to the purpose are used. Have. Specific examples of the semiconductor device of the present invention preferably include a flash memory, DRAM, FRAM, MOS transistor, and the like. The semiconductor device of the present invention can be suitably manufactured by the method for manufacturing the semiconductor device of the present invention described below.

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

In the resist pattern forming step, after forming a resist pattern on the base layer, the resist pattern thinning material of the present invention is applied so as to cover the surface of the resist pattern, and the resist pattern is coated on the surface of the resist pattern. This is a step of forming a resist pattern in which the resist pattern is thinned by developing a mixing layer of the material and the resist pattern thinning material. Examples of the base layer include surface layers of various members in semiconductor devices, and preferred examples include a substrate such as a silicon wafer or a surface layer thereof. The resist pattern is as described above. The coating method is as described above. Further, after the coating, it is preferable to perform the above-mentioned pre-baking, baking and the like.

The patterning step is a step of patterning the base layer by etching using the resist pattern formed in the resist pattern forming step as a mask. The etching method is not particularly limited and may be appropriately selected from known methods depending on the intended purpose. For example, dry etching is preferably used. The etching conditions are not particularly limited and can be appropriately selected depending on the intended purpose.

As the other steps, for example, a surfactant coating step, a developing treatment step and the like are preferably mentioned.

The surfactant coating step is a step of applying the surfactant to the surface of the resist pattern before the resist pattern forming step. The surfactant is as described above, and a nonionic surfactant is preferable, and a polyoxyethylene-polyoxypropylene condensate compound, a polyoxyalkylene alkyl ether compound, a polyoxyethylene alkyl ether compound, and a polyoxyethylene derivative are used. More preferably, it is at least one selected from a compound, a sorbitan fatty acid ester compound, a glycerin fatty acid ester compound, a primary alcohol ethoxylate compound, and a phenol ethoxylate compound.

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

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

(Example 1) -Preparation of resist pattern thinning material-The resist pattern thinning materials A to H of the present invention having the compositions shown in Table 1 were prepared. In Table 1, the unit of the numerical value in parentheses represents the mass part. In the "resin" column, "KW-3" represents a polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.), "PVA" represents a polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., Poval 117), and "PVP" is Represents a polyvinyl phenol resin (manufactured by Maruzen). In the "crosslinking agent" column, "uryl" represents tetramethoxymethylglycoluryl, and "ureia" is N, N'-dimethoxymethyldimethoxyethyleneuria is represented, and "melamine" is hexamethoxymethylmelamine. In the "surfactant" column, "TN-80" represents a nonionic surfactant (manufactured by Asahi Denka Co., Ltd., a polyoxyethylene monoalkyl ether-based surfactant), and "PC-8" is a nonionic surfactant. Represents an ionic surfactant (manufactured by Asahi Denka Co., Ltd., a phenol ethoxylate-based surfactant). Further, as solvent components excluding the water-soluble resin and / or the alkali-soluble resin, the cross-linking agent and the surfactant, pure water (deionized water), isopropyl alcohol (IPA), ethylene glycol (EG), propylene. Glycolmethyl ether (PGME) or the like was used.

<tables num="1"><img file="JP2007017993A_D0001.tif" /></tables>

-Resist pattern and its production-The resist pattern thinning materials A to H of the present invention prepared above are applied by a spin coating method onto an isolated line pattern formed by the ArF resist (manufactured by Sumitomo Chemical Co., Ltd., PAR700). First, apply under the conditions of 1000 rpm / 5s, then at 3500 rpm / 40s, then perform the prebaking under the conditions of 85 ° C / 70s, and then perform the baking under the conditions of 110 ° C / 70s. Rinse the resist pattern thinning materials A to H with pure water or an alkaline developer for 60 seconds, remove the resist pattern thinning material and the mixing layer, and obtain a resist pattern thinned by the resist pattern thinning materials A to H. Manufactured.

The size of the thinned resist pattern is shown in Table 2 together with the initial resist pattern size (the size of the resist pattern before thinning). In Table 2, "A" to "H" correspond to the resist pattern thinning materials A to H.

<tables num="2"><img file="JP2007017993A_D0002.tif" /></tables>

From the results in Table 2, it can be seen that the resist pattern thinning material of the present invention can thin the resist pattern.

Next, the resist pattern thinning materials C and F of the present invention were applied to the surface of the resist formed on the silicon substrate and crosslinked to form a surface layer having a thickness of 0.5 μm. Etching apparatus (parallel plate type RIE apparatus, Fujitsu Limited) for these surface layers, the KrF resist (manufactured by Shipley, UV-6) for comparison, and polymethylmethacrylate (PMMA) for comparison. Pμ = 200W, pressure = 0.02 Torr, CF₄Etching was performed for 3 minutes under the condition of gas = 100 sccm, the amount of film thinning of the sample was measured, the etching rate was calculated, and the relative evaluation was performed based on the etching rate of the KrF resist.

<tables num="3"><img file="JP2007017993A_D0003.tif" /></tables>

From the results shown in Table 3, it can be seen that the etching resistance of the resist pattern thinning material of the present invention is close to that of the KrF resist and is significantly superior to that of the PMMA.

(Example 2)-Manufacturing of MOS transistor- As shown in step (1A) of FIG. 2, a gate oxide film 12 was formed on the surface of the silicon substrate 11, and a polysilicon film (Poly-Si film) 13 was formed on the gate oxide film 12 by the CVD method. After the formation of the Poly-Si film 13, n-type impurities such as phosphorus were injected to reduce the resistance. Then, the WSi film 14 was formed by a sputtering method (may be a CVD method or the like). Next, as shown in step (1B) of FIG. 2, in order to pattern the Poly-Si film 13 and the WSi film 14, a resist film 15 is formed on the WSi film 14 formed in the previous step and patterning is performed. A resist pattern 15a was obtained. Anisometric etching was performed using the formed resist pattern 15a as a mask, and the WSi film 14 and the Poly-Si film 13 were sequentially etched to form a gate electrode composed of the Poly-Si film 13 and the WSi film 14. Then, phosphorus was implanted by ion implantation to form an N-diffusion layer 16 having an LDD structure. After forming the pattern shown in step (1C) of FIG. 2, the resist pattern 15a was peeled off and removed. Following the formation of the gate electrode, as shown in step (1D) of FIG. 2, the oxide film 17 was formed on the entire surface by the CVD method. Next, as shown in step (1E) of FIG. 2, the oxide film 17 was anisotropically etched to form a sidewall 18 on the gate electrode side composed of the Poly-Si film 13 and the WSi film 14. Next, as shown in step (1F) of FIG. 2, ion implantation was performed using the WSi membrane 14 and the sidewall 18 as masks, and N⁺After forming the diffusion layer 19, N⁺In order to activate the diffusion layer 19, heat treatment was performed in a nitrogen atmosphere, and further heating was performed in an oxygen atmosphere. Then, the gate electrode was covered with the thermal oxide film 20. Subsequently, as shown in step (1G) of FIG. 2, the interlayer insulating film 20a was formed by the CVD method, and a resist film was formed on the interlayer insulating film 20a and patterned to obtain a resist pattern. Anisotropic etching was performed using this resist pattern as a mask to open contact holes in the interlayer insulating film 20a. Aluminum wiring 20b was formed in the contact hole to manufacture an N-channel fine MOS transistor. In Example 2, the resist pattern 5a is thinned by using the resist pattern thinning material of the present invention by the same method as in Example 1.

(Example 3) -Manufacture of thin film magnetic head-As shown in step (2A) of FIG. 3, a shield film 22 made of FeN and a gap layer 23 made of a silicon oxide film are sequentially laminated on the altic substrate 21. A magnetoresistive film 24 made of FeNi was formed on the film by a sputtering method. General-purpose PMGI resist film 25 (US Microlithography Chemical) on the magnetoresistive film 24 (Made by Co.) was formed, and a resist film 26 was further formed on the resist film 26 to perform patterning to form a resist pattern 26a. Simultaneously with the formation of the resist pattern 26a, the PMGI resist film 25 was isotropically developed, and as shown in step (2B) of FIG. 3, an undercut-shaped pattern 25a was formed. Next, as shown in step (2C) of FIG. 3, ion milling was performed using the obtained pattern 25a as a mask, and the magnetoresistive film 24 was etched into a damper shape. Next, as shown in step (2D) of FIG. 3, a TiW film 27 was formed on the entire surface to be treated by a sputtering method. Next, when the pattern 25a, the resist pattern 26a, and the TiW film 27 were removed by the lift-off method, the TiW film 27 was exposed as shown in step (2E) of FIG. Then, although not shown, the magnetoresistive film 24 and the TiW film 27 were patterned in the same manner as described above, and then the electrode 28 and the MR element 29 were formed as shown in the step (2F) of FIG. Next, as shown in step (2G) of FIG. 3, SiO is applied to the entire surface to be treated.₂A gap insulating layer 31 made of a film was formed. Next, as shown in step (2H) of FIG. 3, following the formation of the gap insulating layer 31, the shield film 32 and Al made of FeNi film on the entire surface thereof.₂O₃The gap layer 33 made of a film was sequentially formed, and the FeNi layer 34 was further formed on the gap layer 33. Next, a resist film 36 was formed on the entire surface of the FeNi film 34 and patterned to form a resist pattern in which the portion of the light electrode was opened. Using this pattern as a mask, the FeNi film was isotropically etched to produce a thin film magnetic head provided with the light electrode 35 as shown in step (2I) of FIG. In Example 3, the resist pattern 26a is thinned by using the resist pattern thinning material of the present invention by the same method as in Example 1.

Here, a preferred embodiment of the present invention will be added as follows. (Appendix 1) A resist pattern thinning material containing at least one selected from a water-soluble resin and an alkali-soluble resin. (Appendix 2) The resist pattern thinning material according to Appendix 1, which contains a water-soluble resin and has a coating film having a dissolution rate of 10 Å / s or more in water at 25 ° C. (Appendix 3) The resist pattern thinning material according to Appendix 1, which contains a water-soluble resin and has a coating film having a dissolution rate of 50 to 1000 Å / s in water at 25 ° C. (Appendix 4) The resist pattern thinning material according to any one of Appendix 1 to 3, which shows water solubility in which a water-soluble resin dissolves 0.1 g or more in 100 g of water at 25 ° C. (Appendix 5) The water-soluble resin is at least one selected from polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine, polyethylene oxide, polyacrylic acid, polyvinylamine and polyacrylamide. The resist pattern thinning material according to any one. (Appendix 6) The resist pattern thinning material according to Appendix 1, which contains an alkali-soluble resin and has a coating film having a dissolution rate of 10 Å / s or more in a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. (Appendix 7) The resist pattern thin-walled according to Appendix 1 or 6, which contains an alkali-soluble resin and whose coating film has a dissolution rate of 50 to 1000 Å / s in a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. Chemical material. (Appendix 8) The resist pattern thinning material according to any one of Appendix 1 and 6 to 7, which indicates alkali solubility in which an alkali-soluble resin dissolves 0.1 g or more in 100 g of a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ° C. .. (Appendix 9) At least one alkali-soluble resin selected from acrylic acid, methacrylic acid, itaconic acid, vinylbenzoic acid, vinylphenol, styrene, polyhydric phenol, polyhydric alcohol and derivatives thereof is used as a monomer unit. The resist pattern thinning material according to any one of Appendix 1 and 6 to 8 having one. (Appendix 10) The alkali-soluble resin is at least one selected from novolak resin, vinylphenol resin, polyacrylic acid, polymethacrylic acid, polyp-hydroxyphenylacrylate, polyp-hydroxyphenylmethacrylate, and copolymer resins thereof. The resin pattern thinning material according to any one of Appendix 1 and 6 to 9. (Appendix 11) The resist pattern thinning material according to any one of Appendix 1 to 10, which contains a cross-linking agent. (Supplementary note 12) The resist pattern thinning material according to any one of Supplementary notes 1 to 11, wherein the cross-linking agent is at least one selected from a melamine derivative, a urea derivative and a uryl derivative. (Appendix 13) The resist pattern thinning material according to any one of Appendix 1 to 12, which contains a surfactant. (Appendix 14) The surfactants are polyoxyethylene-polyoxypropylene condensate compound, polyoxyalkylene alkyl ether compound, polyoxyethylene alkyl ether compound, polyoxyethylene derivative compound, sorbitan fatty acid ester compound, glycerin fatty acid ester compound, and primary alcohol. The resist pattern thinning material according to Appendix 13, which is at least one selected from an ethoxylate compound and a phenol ethoxylate compound. (Appendix 15) The resist pattern thinning material according to any one of Appendix 1 to 14, which contains a solvent. (Appendix 16) The resist pattern thinning material according to Appendix 15, wherein the solvent is at least one selected from water, an alcohol-based solvent, and a glycol-based solvent. (Appendix 17) After forming the resist pattern, the resist pattern thinning material according to any one of Appendix 1 to 16 is applied so as to cover the surface of the resist pattern, and the material of the resist pattern is applied to the surface of the resist pattern. A method for producing a resist pattern, which comprises at least forming a mixing layer between the resist pattern and the resist pattern thinning material. (Appendix 18) Resist pattern The method for producing a resist pattern according to Appendix 17, wherein a thinning material is applied and then a developing process is performed. (Appendix 19) The method for producing a resist pattern according to Appendix 18, wherein the development process is performed using at least one of water and an alkaline developer. (Appendix 20) A resist pattern obtained by the method for producing a resist pattern according to any one of Appendix 17 to 19. (Appendix 21) A semiconductor device characterized in that it is formed by using the pattern formed by the resist pattern described in Appendix 20. (Appendix 22) After forming a resist pattern on the base layer, the resist pattern thinning material according to any one of Appendix 1 to 16 is applied so as to cover the surface of the resist pattern, and the surface of the resist pattern is covered with the resist pattern thinning material. A resist pattern forming step of forming a resist pattern in which the resist pattern is thinned by forming a mixing layer of the resist pattern material and the resist pattern thinning material and then developing the resist pattern, and etching using the resist pattern as a mask. A method for manufacturing a semiconductor device, which comprises a patterning step of patterning the underlying layer.

The resist pattern and its manufacturing method of the present invention include, for example, mask patterns, reticle patterns, magnetic heads, LCDs (liquid crystal displays), PDPs (plasma display panels), SAW filters (elastic surface wave filters) and other functional components, and optical wiring. It can be suitably used for manufacturing optical parts used for connecting the above, fine parts such as microactuators, semiconductor devices, and the like. The semiconductor device and its manufacturing method of the present invention can be used as various semiconductor devices such as flash memory, DRAM, FRAM, MOS transistor, etc., or can be used for efficient manufacturing thereof.

<figref num="1">FIG. 1 is a schematic view for explaining a mechanism of thinning a resist pattern (inner layer rangest pattern) using the resist pattern thinning material of the present invention.</figref><figref num="2">FIG. 2 is a process diagram for explaining an example in which a resist pattern thinned by using the resist pattern thinning material of the present invention is applied to the manufacture of a MOS transistor which is a semiconductor device.</figref><figref num="3">FIG. 3 is a process diagram for explaining an example in which the resist pattern thinned by using the resist pattern thinning material of the present invention is applied to the production of a thin film magnetic head.</figref>

Code description

1 Semiconductor substrate 2 Resist film 2a Resist pattern 2b Thinning resist pattern 3 Resist pattern Thinning material 4 Mixing layer 5 Underlayer (base material) 11 Si substrate (semiconductor substrate) 12 Gate oxide film 13 polysilicon film (Poly-Si film) ) 14 WSi film 15 resist film 15a resist pattern 16 N-diffusion layer 17 oxide film 18 sidewall 19 N⁺Diffusion layer 9 20 Thermal oxide film 20a Interlayer insulation film 20b Aluminum wiring 21 Altic substrate 22 Shield film 22 23 Gap layer 24 Magnetic resistance effect film 25 PMGI Resist film 25a Pattern 26 Resist film 26a Resist pattern 27 TiW film 28 Electrode 29 MR element 31 Gap insulation layer 32 shield film 33 gap layer 34 FeNi layer 35 light electrode 36 resist film