Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/146—Laser beam

Definitions

• the present invention relates to a protective film forming material used for providing a protective film on a photoresist film, a method of forming a photoresist pattern using this protective film forming material, and a method of forming this photoresist pattern.
• the present invention relates to a protective film cleaning and removing solution.
• the protective film forming material in the present invention includes at least a protective film forming material used in a normal dry exposure process and a protective film forming material used in an immersion exposure process.
• the protective film forming material used in the normal dry exposure process described above is a protective film used mainly for the purpose of suppressing a photogas that also generates a photoresist film force when performing pattern formation by photolithography technology. It is a material for forming a film.
• the material for forming a protective film used in the immersion exposure process has a refractive index higher than that of air and a refractive index higher than that of the photoresist film on at least the photoresist film in the path through which the lithography exposure light reaches the photoresist film.
• This is a material for forming a protective film suitable for use in an immersion exposure optical process in which the resolution of a photoresist pattern is improved by exposing the photoresist film in a state where a liquid having a low predetermined thickness is interposed.
• This multiple interference of light is caused by the light energy absorbed in the thickness direction of the photoresist film when the single wavelength irradiation light incident on the photoresist film formed on the substrate interferes with the reflected light from the substrate.
• This difference is caused by the difference in the amount of photoresist, and variations in the photoresist film thickness affect the width of the resist pattern obtained after development, resulting in a decrease in the dimensional accuracy of the photoresist pattern.
• a resin composition containing a material that absorbs exposure light is applied on the substrate to form a lower layer film (antireflection film).
• a method of forming a photoresist film on this lower layer film see Patent Document 1
• a water-soluble resin film such as polysiloxane or polybutyl alcohol as an antireflection film on the photoresist film provided on the substrate.
• the forming method is adopted (see Patent Documents 2 and 3)
• Non-Patent Document 1 "Journal 'Ob' Vacuum 'Science' And 'Technology B (Jo urnal of Vacuum Science & Technology B) ", (USA), 1999, Vol. 17, No. 6, pp. 3306-3309
• Non-Patent Document 2 "Journal of Vacuum Science & Technology B” (USA), 2001, Vol. 119, No. 6, pages 2353-2356
• Non-Patent Document 3 "Proceedings of SPI"
• Patent Document 1 U.S. Pat.No. 4,910,122
• Patent Literature 2 Japanese Patent Publication No. 4 55323
• Patent Document 3 Japanese Patent Laid-Open No. 3-222409
• Patent Document 4 International Publication No. 2004/068242 Pamphlet
• Patent Document 5 International Publication No. 2004/074937 Pamphlet
• Patent Document 6 Japanese Unexamined Patent Application Publication No. 2005-264131
• Patent Document 5 requires a fluorine-based special solvent.
• This fluorine-based special solvent has a problem that it has a large impact on the environment, such as a high global warming potential.
• the protective film disclosed in Patent Document 6 may cause mixing with the underlying photoresist film, and there is a problem in forming a photoresist pattern having a desired resolution.
• An object of the present invention is to provide a protective film-forming material which has water repellency and can form a high-resolution photoresist pattern when mixing with a photoresist film occurs. It is another object of the present invention to provide a method for forming a photoresist pattern using a protective film formed from this protective film forming material, and a protective film cleaning and removing solution.
• the present inventors have found that the above object can be achieved by using a protective film-forming material containing a nonpolar polymer and a nonpolar solvent, and have completed the present invention.
• the present invention is a protective film forming material for forming a protective film laminated on a photoresist film, comprising (a) a nonpolar polymer and (b) a nonpolar solvent.
• a protective film-forming material characterized by the above is provided.
• the present invention also provides a photoresist pattern forming method
• the present invention also provides a photoresist pattern forming method using an immersion exposure process.
• a method of forming a photoresist pattern comprising: developing the photoresist film using an alkaline developer, and developing the photoresist film.
• the present invention is a protective film cleaning / removing liquid used in the photoresist pattern forming method, wherein the protective film cleaning / removing liquid is at least one selected from hydrocarbon solvents.
• a protective film cleaning solution is provided.
• the protective film forming material used in the dry exposure process can effectively suppress outgas from the photoresist film without causing characteristic deterioration of the photoresist film.
• the protective film forming material used in the immersion exposure process has a high water repellency that has a small impact on the environment, and forms a high-resolution photoresist pattern that is unlikely to mix with the photoresist film. It becomes possible. Further, by forming a photoresist pattern using this protective film, it becomes possible to form a photoresist pattern with higher resolution than before.
• component (b) a nonpolar solvent
• Non-polar polymers are polar groups in the molecule (OH, -NO, -CO, -NH, -O
• ⁇ nonpolar polymer As a first embodiment of the ⁇ nonpolar polymer, a polymer having a monomer unit represented by the following general formula (A-1) as a structural unit can be used.
• a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (however, part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms).
• Z is an alkylene chain having 1 to 2 carbon atoms or an oxygen atom, and n is an integer of 0 to 3.
• alkyl groups of R and R specifically, methyl group, ethyl group, n-propyl group
• a linear alkyl group such as n-butyl group and n-pentyl group, a branched alkyl group such as isopropyl group, 1-methylolpropyl group, 2-methylpropyl group and tert-butyl group, cyclopentyl group, cyclo Examples thereof include cyclic alkyl groups such as a hexyl group. Some or all of the hydrogen atoms of these alkyl groups may be substituted with fluorine atoms.
• Z is preferably a methylene chain, and n is preferably 0.
• the (a) nonpolar polymer according to the present invention is a monomer unit represented by the general formula ( ⁇ -1), a plurality of types having different substituents which may be homopolymers, or other
• the non-polar polymer may be a copolymer polymerized between one another.
• Such a non-polar polymer (a) can be synthesized by a known method. Further, the polystyrene equivalent weight average molecular weight (Mw) of this polymer by GPC is not particularly limited, but is preferably 2000 force, etc., 80,000, 3000 force, etc., more than 50000.
• the content be about 1% to 20% by mass. 0.3% to 10% by mass Are more preferable.
• a nonpolar polymer As another embodiment of the (a) nonpolar polymer, a cyclic olefin-based polymer copolymer other than those described above can be used.
• Examples of such cyclic olefin-based polymers other than those described above include, for example, the APPEL series (trade name: manufactured by Mitsui Chemicals), the ZEONOR series, and the ZEONEX series (all of the commercially available products). Zeon Corporation), TOPAS Series (TICONA Corporation), etc.
• the nonpolar solvent is not particularly limited as long as it can dissolve the component (a), does not react with the photoresist film, and has little environmental impact.
• a hydrogen-based solvent is preferred.
• hydrocarbon solvent examples include hydrocarbons such as hexane, heptane, octane, nonane, methenoleoctane, decane, undecane, dodecane, and tridecane, branched hydrocarbons having 3 to 15 carbon atoms, benzene, toluene, Examples thereof include aromatic hydrocarbons such as tilbenzene and hydrocarbons having a cyclic skeleton such as terpene solvents. These can be used alone or in combination of two or more.
• a terpene solvent that is a hydrocarbon having a cyclic skeleton.
• terpene solvents include geraniol, nerol, linalool nore, citranore, citronellore, ⁇ -menthane, ⁇ -menthane, m-menthane, dipheninolementane, mentholore, isomenthenol, neomenthenol, limonene, ⁇ -tenolepinene, Te-norevinen, ⁇ -terbinene, ⁇ -terpineol, / 3-tervineol, ⁇ -tervineol, terpinene 1-honore, terpinene 4-ol, 1,4-terpin, 1,8-terpine, carvone, leon, gyon, Monoters such as camphor, bornan, borneo noreno, norbornorenan, pin
• Pens, And diterpenes such as abietane and abietic acid. Of these, monoterpenes are preferred because they are easily available. Among them, at least one selected from limonene, vinylene, and ⁇ -menthane is preferable because of its high solubility. [0031] [Method of forming photoresist pattern]
• the photoresist pattern forming method according to the present invention can be divided into a photoresist pattern forming method using a dry exposure process and a photoresist pattern forming method using an immersion exposure process.
• a method for forming a photoresist pattern by an immersion exposure process according to the present invention includes:
• step (1) a step of providing a photoresist film on a substrate (hereinafter also referred to as step (1));
• step (2) forming a protective film on the photoresist film using the protective film forming material (hereinafter also referred to as step (2));
• step ( 3) A step of disposing an immersion exposure liquid on at least the protective film of the substrate, and selectively exposing the photoresist film through the immersion exposure liquid and the protective film (hereinafter referred to as the step ( 3))
• step (4) a step of removing the protective film using a protective film cleaning solution containing a nonpolar organic solvent (hereinafter also referred to as step (4));
• step (5) a step of developing the photoresist film using an alkali developer (hereinafter also referred to as step (5)).
• Step (1) is a step of providing a photoresist film on the substrate.
• a known photoresist composition is applied to a substrate such as a silicon wafer by using a known method such as a spinner, and then pre-beta (PAB treatment) is performed to form a photoresist film.
• a photoresist film may be formed after an organic or inorganic antireflection film (lower antireflection film) is provided on the substrate.
• Step (2) is a step of forming a protective film on the photoresist film.
• the protective film-forming material according to the present invention prepared at a predetermined concentration is uniformly applied to the surface of the photoresist film formed in the step (1) by the same method as in the step (1).
• a protective film is formed by curing with beta.
• step (3) an immersion exposure medium is disposed on the protective film, and in this state, the photoresist film and the protective film on the substrate are selectively exposed through the mask pattern.
• the exposure light passes through the immersion exposure liquid and the protective film and reaches the photoresist film.
• the photoresist film is shielded from the immersion exposure liquid by the protective film. Therefore, the liquid is exposed to the invasion of the immersion exposure liquid and suffers alteration such as swelling, or conversely, the components are eluted in the immersion exposure liquid and the optical characteristics such as the refractive index of the immersion exposure liquid itself. It is possible to prevent alteration of the material.
• the exposure light is not particularly limited as in the dry exposure process, and can be performed using radiation such as ArF excimer laser, KrF excimer laser, EUV, VUV (vacuum ultraviolet).
• the immersion exposure liquid is not particularly limited as long as it has a refractive index larger than that of air and smaller than that of the photoresist film to be used.
• immersion exposure liquids include water (pure water, deionized water), fluorinated inert liquids, etc., and immersion exposure with high refractive index characteristics that are expected to be developed in the near future.
• a working liquid can also be used.
• fluorinated inert liquids include C HC1 F, C F OCH
• water pure water, deionized water
• pure water deionized water
• the substrate is taken out of the immersion exposure liquid and the liquid is removed from the substrate.
• step (4) a heat treatment is performed as necessary while a protective film is laminated on the photoresist film after the exposure through the above step (3), and a non-polar organic solvent described later is used.
• Protective film cleaning is a step of removing the protective film using a removing solution.
• the mixing layer is formed by mixing the protective film and the photoresist film.
• Step (5) is a step of developing the photoresist film using an alkali developer.
• an alkali developer a known developer can be appropriately selected and used. Since the protective film has been removed by the above step (4), it is the photoresist film that is removed by this developer.
• rinsing is performed using pure water or the like. This water rinse, for example, does not rotate the substrate. Then, water is dropped or sprayed on the surface of the substrate to wash away the developer on the substrate and the protective film component and the photoresist composition dissolved by the developer. By performing drying, a photoresist pattern in which the photoresist film is patterned into a shape corresponding to the mask pattern is obtained.
• the protective film formed of the protective film-forming material according to the present invention in the liquid immersion light exposure process, since it has high water repellency, the liquid for liquid immersion exposure after the exposure is completed. The so-called liquid leakage for immersion exposure is reduced because the amount of the liquid for immersion exposure that is easily separated is small.
• the method for forming a photoresist pattern by the dry exposure process according to the present invention is common to the immersion exposure process except that the immersion exposure liquid is not used.
• the protective film formed of the material for forming a protective film according to the present invention in the dry exposure process, the photoresist film strength and other outgases are not effectively deteriorated with respect to the photoresist film. Can be suppressed.
• the conventional protective film absorbs EUV exposure light
• the protective film formed of the protective film forming material according to the present invention does not absorb EUV exposure light and outgas from the photoresist film.
• the protective film-forming material according to the present invention is particularly useful for a dry exposure process using EUV as exposure light because it can suppress the contamination of the exposure apparatus.
• the protective film washing and removing liquid according to the present invention is not particularly limited as long as it contains a nonpolar organic solvent and can dissolve the protective film formed of the protective film forming material according to the present invention. Is not to be done.
• the hydrocarbon solvent preferably contains a hydrocarbon solvent, for example, hydrocarbons such as hexane, heptane, octane, nonane, methenoleoctane, decane, undecane, dodecane, tridecane, etc. Examples thereof include 3 to 15 branched hydrocarbons, aromatic hydrocarbons such as benzene, toluene and jetylbenzene, and hydrocarbons having a cyclic skeleton such as terpene solvents.
• a terpene solvent that is a hydrocarbon having a cyclic skeleton.
• terpene solvents include geraniol, nerol, linalool, citruranole, citronellore, p-menthane, o-menthan, m-menthane, dipheninorementane, mentholenol, isomenthenol, neomenthenol, limonene, ⁇ -tenolepinene, ⁇ -Terevinen, ⁇ -Terbinene, ⁇ -Tervineol, / 3-Tervineol, ⁇ -Tervineeol, Terpinene 1-Honore, Terpinene 4-ol, 1,4-Terpin, 1,8-Terpin, Carvone, Youngon, Gyeon, Monoters such as camphor, bornan, borne
• Pens, Bietan include diterpenes such as Abiechin acid. Of these, monoterpenes are preferred because they are easily available. Among them, at least one selected from limonene, vinylene, and ⁇ -menthane is preferable because of its high cleaning performance.
• a known surfactant or the like may be appropriately blended so as not to impair the properties of the protective film cleaning and removing liquid according to the present invention.
• any photoresist composition that can be developed with an aqueous alkaline solution including negative and positive photoresist compositions, which are not particularly limited, can be used.
• a photoresist composition include (i) a positive photoresist composition containing a naphthoquinone diazide compound and a nopolac resin, (ii) a compound that generates an acid upon exposure, and decomposes with the acid to increase the solubility in an alkaline aqueous solution.
• the composition S, and (iv) a force S including, but not limited to, a negative photoresist composition containing a compound that generates an acid by light, a crosslinking agent and an alkali-soluble resin, are not limited thereto.
• Nonpolar polymer having a monomer unit represented by the following structural formula (X-1) as a structural unit 1 (mass average molecular weight: 12000) was dissolved in p-menthane to prepare a protective film-forming material 1 having a solid content concentration of 1.5 mass%.
• TArF-6a239 manufactured by Tokyo Ohka Kogyo Co., Ltd.
• ARC29 manufactured by Brewer
• 120 ° Heat at C for 60 seconds to form a 150 nm thick photoresist film and apply the above protective film forming material 1 on top of it, and heat at 90 ° C for 60 seconds to protect 35 nm thick A film was formed.
• This substrate was subjected to pattern exposure using NSR-S302A (manufactured by Nikon Corp.) and heated after exposure at 110 ° C for 60 seconds. Subsequently, the protective film was removed using p-menthane. Subsequently 2.38 wt 0/0 tetramethylammonium Niu beam hydroxide for 30 seconds and developed treatment with an aqueous solution, by performing a rinsing process, to form a photoresist pattern. As a result of observing this photoresist pattern with a scanning electron microscope (SEM), the pattern shape was a good rectangular shape.
• SEM scanning electron microscope
• An alkali-soluble polymer (mass average molecular weight: 5000) represented by the following general formula (X-2) was dissolved in dibutyl ether to prepare a protective film-forming material 2 having a solid content concentration of 1.5 mass%.
• the substrate was subjected to pattern exposure using NSR-S302A (manufactured by Nikon Corporation), and was heated after exposure at 110 ° C for 60 seconds.
• the protective film was removed using p-menthane.
• 2.38 wt 0/0 tetramethylammonium Niu beam hydroxide for 30 seconds and developed treatment with an aqueous solution, by performing a rinsing process, to form a photoresist pattern.
• SEM scanning electron microscope
• Nonpolar polymers shown in Table 1 below were each dissolved in p-menthane to prepare a protective film-forming material having a solid content concentration of 1.2% by mass.
• TDUR-P628 manufactured by Tokyo Ohka Kogyo Co., Ltd.
• a photoresist for KrF containing polyhydroxystyrene resin was applied onto a 6-inch silicon wafer and heated at 130 ° C for 90 seconds.
• a photoresist film having a thickness of 800 nm was formed, and each of the prepared protective film forming materials was applied to the upper layer and heated at 90 ° C. for 90 seconds to form a protective film having a thickness of 30 nm.
• Each of the above silicon wafers is in the exposure apparatus "VUVES-4500" (manufactured by RISOTEC JAPAN) Placed on. Further, a nitrogen gas having a flow rate of 1. OL / cm 2 is allowed to flow from the intake port of the exposure apparatus, and the nitrogen gas exhausted from the exhaust port is collected by a collection device “Automated Thermal Desorber Turbo Matrix ATD (manufactured by PerkinElmer Instruments) (capture). Collected by Tenax TA: manufactured by SUP ELCO], and the amount of thioadisol in the collected gas components was measured. The detected amount of thioanisole was shown as a relative ratio when the amount of thioanisole in Comparative Example 2 in which no protective film was provided was 100%. The results are shown in Table 1.

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• Engineering & Computer Science (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
• Materials For Photolithography (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

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