WO2023199659A1 - レジスト材料、レジストパターンの製造方法、及び、レジストパターン - Google Patents

レジスト材料、レジストパターンの製造方法、及び、レジストパターン Download PDF

Info

Publication number
WO2023199659A1
WO2023199659A1 PCT/JP2023/009016 JP2023009016W WO2023199659A1 WO 2023199659 A1 WO2023199659 A1 WO 2023199659A1 JP 2023009016 W JP2023009016 W JP 2023009016W WO 2023199659 A1 WO2023199659 A1 WO 2023199659A1
Authority
WO
WIPO (PCT)
Prior art keywords
resist
resist pattern
exposure
extreme ultraviolet
ultraviolet rays
Prior art date
Application number
PCT/JP2023/009016
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
公男 吉村
亮 出崎
洋揮 山本
タンフン ヂン
雅彦 石野
将元 錦野
康成 前川
孝弘 古澤
Original Assignee
国立研究開発法人量子科学技術研究開発機構
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立研究開発法人量子科学技術研究開発機構 filed Critical 国立研究開発法人量子科学技術研究開発機構
Publication of WO2023199659A1 publication Critical patent/WO2023199659A1/ja

Links

Images

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
    • 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
    • G03F7/075—Silicon-containing compounds
    • 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

Definitions

  • the present invention relates to a resist material, a method for manufacturing a resist pattern, and a resist pattern.
  • Photolithography is widely used in which a photomask is two-dimensionally patterned with areas that transmit light and areas that do not transmit light, and the pattern of the photomask is transferred to a photoresist layer.
  • the fineness of the pattern that can be transferred using photolithography depends on the wavelength of the light used for exposure. Theoretically, the shorter the wavelength of the light used for exposure, the finer the pattern can be transferred to the photoresist layer. Therefore, when attempting to transfer a pattern as fine as possible using photolithography, ultraviolet rays (for example, wavelengths of 193 nm, 248 nm, etc.) are often used as light for exposure. Such photolithography is called ultraviolet (UV) lithography.
  • UV ultraviolet
  • the width of a thin line that can be transferred using UV lithography is, for example, 18 nm (see, for example, Patent Document 1).
  • EB lithography has become popular as a form of lithography different from photolithography.
  • an electron beam having a shorter wavelength than ultraviolet light for example, a wavelength of 1 nm
  • the resist layer is exposed by irradiating the resist layer with a focused electron beam while scanning it in a desired pattern.
  • the width of a thin line that can be drawn using EB lithography is, for example, 10 nm (see, for example, Patent Document 2).
  • EUV extreme ultraviolet
  • a photoresist layer can be exposed using a photomask while using light with a shorter wavelength than in UV lithography. Therefore, a pattern with higher definition than UV lithography can be obtained with a shorter exposure time than EB lithography.
  • a photoresist material is a photoresist material for extreme ultraviolet lithography, and is one of polycarbosilane, polysiloxane, polysilazane, and polyorganobolosilazane. Contains a polymer alloy containing at least one of these or a metal alkoxide.
  • a method for manufacturing a resist pattern uses a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganobolosilazane, or A coating step of applying a resist material containing a metal alkoxide onto a substrate, an exposure step of bringing a photomask close to the substrate coated with the resist material and exposing the resist material, and developing the exposed resist material. A developing step.
  • a resist pattern according to one embodiment of the present invention is an amorphous film made of at least one of silicon carbide, silicon dioxide, silicon nitride, and borosilicon carbonitride, It consists of an amorphous film patterned two-dimensionally.
  • a resist material having high dry etching resistance can be provided. Furthermore, it is possible to provide a method for manufacturing a resist pattern using such a resist material, and a resist pattern.
  • FIG. 7 is a flowchart of a resist pattern manufacturing method M10 according to Embodiment 3 of the present invention.
  • 7 is a flowchart of a resist pattern manufacturing method M20 according to Embodiment 4 of the present invention.
  • FIG. 7 is a diagram showing a resist pattern 1 according to Embodiment 5 of the present invention.
  • FIG. 3 is a diagram showing a sensitivity curve created by measuring the film thickness of the remaining pattern in the samples of Examples 1 and 2 that were subjected to EB irradiation or EUV irradiation.
  • FIG. 7 is a diagram showing a sensitivity curve created by measuring the film thickness of the remaining pattern in the samples of Examples 3 to 5 that were subjected to EB irradiation or EUV irradiation.
  • FIG. 3 is a diagram showing a resist film before and after firing conversion.
  • FIG. 3 is a diagram showing the etching resistance of Example 2 after development or baking conversion, and Comparative Example 1 after coating.
  • FIG. 3 is a diagram showing the etching resistance of Examples after development or baking conversion, and Comparative Examples after coating.
  • (a) is the etching resistance of Example 3 and Comparative Examples 1 to 4
  • (b) is the etching resistance of Example 4 and Comparative Examples 1 to 4
  • (c) is Example 5 and Comparative Examples 1 to 4. shows etching resistance.
  • a resist pattern of Example 2 produced by irradiating pulsed EUV is shown.
  • a resist pattern of Example 5 produced by irradiating pulsed EUV is shown.
  • the photoresist material according to Embodiment 1 of the present invention is a photoresist material for extreme ultraviolet lithography, and includes a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane. include.
  • silicon carbide or the like is converted into a ceramic by crosslinking or firing conversion by irradiation with extreme ultraviolet rays. Therefore, by exposing the photoresist material according to this embodiment to extreme ultraviolet rays, a resist pattern made of ceramics such as silicon carbide can be obtained.
  • a resist pattern made of ceramics such as silicon carbide has higher density and hardness than a resist pattern made of a conventionally used polymer resin. Therefore, a resist pattern made of ceramics such as silicon carbide has higher dry etching resistance than a resist pattern made of polymer resin. Therefore, according to the present resist material, a photoresist material having high dry etching resistance can be provided.
  • the photoresist material according to the present embodiment is crosslinked or converted by baking when irradiated with extreme ultraviolet rays, a strong network can be constructed.
  • "calcination conversion” refers to converting an organic substance into an inorganic substance by calcination. Therefore, the photoresist material according to this embodiment can prevent evaporation of the photoresist material even when exposed using high-intensity extreme ultraviolet rays such as pulsed extreme ultraviolet rays.
  • pulsed extreme ultraviolet light refers to extreme ultraviolet light whose waveform has an extremely narrow half-width when viewed along the time axis. In this specification, pulsed extreme ultraviolet rays refer to extreme ultraviolet rays whose half-width is 1 nanosecond or less.
  • Such pulsed extreme ultraviolet rays have a very high intensity per pulse.
  • the intensity per pulse of the pulsed extreme ultraviolet rays is not limited, but is, for example, 10 9 W/cm 2 or more and 10 14 W/cm 2 or less.
  • the photoresist material according to this embodiment can prevent evaporation of the photoresist material even when exposed using such high-intensity pulsed extreme ultraviolet rays. Therefore, when exposing using high-intensity pulsed extreme ultraviolet rays, the photoresist material according to this embodiment can shorten the exposure time.
  • polymer alloy contains at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane.
  • polymer alloy means a polymer multicomponent system, and includes a mixture of a polymer and a monomer having a double bond.
  • Polycarbosilane is a polymer whose main chain is a skeleton in which silicon atoms and carbon atoms are alternately bonded.
  • the main chain may be linear, branched or cyclic, and may have a three-dimensional crosslinked structure.
  • the substituent on the polycarbosilane may have any structure as long as it does not impair the effects of the present invention. Examples of the substituent include, in addition to hydrogen, a methyl group, a benzene ring, a benzene derivative, or a carbon chain having two or more carbon atoms that may contain a hetero atom.
  • the heteroatom is preferably selected from boron (B), nitrogen (N), oxygen (O), phosphorus (P), and sulfur (S).
  • the polycarbosilane preferably has a molecular weight of 200 or more and 40,000 or less.
  • the molecular weight is less than 200, evaporation in vacuum tends to occur, and when it is more than 40,000, the volume of the polymer chain becomes large, making it difficult to obtain a fine pattern.
  • allylhydridopolycarbosilane is preferred among carbosilanes.
  • Polysiloxane is a polymer whose main chain is a skeleton in which silicon atoms and oxygen atoms are alternately bonded.
  • the main chain may be linear, branched or cyclic, and may have a three-dimensional crosslinked structure.
  • the substituent on the polysiloxane may have any structure as long as it does not impair the effects of the present invention. Examples of the substituent include, in addition to hydrogen, a methyl group, a benzene ring, a benzene derivative, or a carbon chain having two or more carbon atoms that may contain a hetero atom.
  • the polysiloxane preferably has a molecular weight of 200 or more and 40,000 or less. When the molecular weight is less than 200, evaporation in vacuum tends to occur, and when it is more than 40,000, the volume of the polymer chain becomes large, making it difficult to obtain a fine pattern.
  • Polysilazane is a polymer whose main chain is a skeleton in which silicon atoms and nitrogen atoms are alternately bonded.
  • the main chain may be linear, branched or cyclic, and may have a three-dimensional crosslinked structure.
  • the substituent on polysilazane may have any structure as long as it does not impair the effects of the present invention. Examples of the substituent include, in addition to hydrogen, a methyl group, a benzene ring, a benzene derivative, or a carbon chain having two or more carbon atoms that may contain a hetero atom.
  • the polysilazane preferably has a molecular weight of 200 or more and 40,000 or less. When the molecular weight is less than 200, evaporation in vacuum tends to occur, and when it is more than 40,000, the volume of the polymer chain becomes large, making it difficult to obtain a fine pattern.
  • Polyorganobolosilazane is a polymer whose main chain is a skeleton consisting of a combination of silicon-nitrogen-silicon, silicon-nitrogen-boron, and boron-nitrogen-boron.
  • the main chain may be linear, branched or cyclic, and may have a three-dimensional crosslinked structure.
  • the substituent on the polyorganoborosilazane may have any structure as long as it does not impair the effects of the present invention. Examples of the substituent include, in addition to hydrogen, a methyl group, a benzene ring, a benzene derivative, and a carbon chain having two or more carbon atoms that may contain a hetero atom.
  • the polyorganobolosilazane preferably has a molecular weight of 200 or more and 40,000 or less.
  • the molecular weight is less than 200, evaporation in vacuum tends to occur, and when it is more than 40,000, the volume of the polymer chain becomes large, making it difficult to obtain a fine pattern.
  • the polymer alloy may contain other polymers and monomers in addition to at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane.
  • examples include polymers containing antioxidants and light stabilizers, resist materials, and nanoparticles (metal oxide precursors) that are coordination-stabilized with high-boiling monomers and vinyl monomers described below.
  • polycarbosilane and allylhydridopolycarbosilane are employed as the polymers constituting the polymer alloy.
  • the structure of polycarbosilane is shown in the following general formula (I)
  • the structure of allylhydridopolycarbosilane is shown in the following general formula (II).
  • 1 wt % allylhydridopolycarbosilane is added to polycarbosilane and dissolved in cyclohexane.
  • a polymer alloy is produced by stirring a cyclohexane solution containing polycarbosilane and allylhydridopolycarbosilane for 10 minutes, and then removing the cyclohexane.
  • a photoresist solution is prepared by dissolving the obtained polymer alloy in toluene at a concentration of 5 wt%.
  • the photoresist solution configured in this manner can be used in photolithography, including spin coating, exposure, and development on a substrate.
  • the ratio of allylhydridopolycarbosilane to polycarbosilane is preferably 0.1 wt% or more and 50 wt% or less, and 1 wt% or more and 10 wt%. % or less is more preferable.
  • a resist pattern is obtained in which the photoreaction progresses in the exposed area and does not progress in the area shielded by the photomask, and which can be exposed with a realistic exposure time. be able to.
  • the term "photoreaction” refers to the formation of crosslinks in the resist material by exposure to light or conversion by firing.
  • the polymer alloy can be obtained using a known production method. For example, it can be obtained by dissolving it in an organic solvent, stirring it, and then removing the organic solvent.
  • the organic solvent is preferably a solvent that dissolves the polymer contained in the polymer alloy, and can be appropriately selected by those skilled in the art depending on the polymer used.
  • the film thickness of the photoresist material coated on the substrate is determined from the viewpoint of forming a high-definition resist pattern and suppressing peeling of the resist pattern.
  • the thickness is preferably 10 nm or more and 250 nm or less.
  • the wavelength is 250 nm or more, effects such as crosslinking due to exposure do not reach the substrate, and peeling and chipping are likely to occur during development.
  • a photoresist material according to Embodiment 2 of the present invention is a photoresist material for extreme ultraviolet lithography, and includes a metal oxide precursor.
  • the metal oxide is converted into a ceramic by crosslinking or firing conversion by irradiation with extreme ultraviolet rays. Therefore, by exposing the photoresist material according to this embodiment to extreme ultraviolet rays, a resist pattern made of metal oxide ceramics can be obtained.
  • a resist pattern made of metal oxide ceramics has higher hardness than a resist pattern made of a conventionally used polymer resin. Furthermore, because the film density increases through crosslinking or firing conversion, and at the same time it becomes inorganic ceramic, a resist pattern made of metal oxide ceramics has higher dry etching resistance than a resist pattern made of polymer resin. Therefore, according to the present resist material, a photoresist material having high dry etching resistance can be provided.
  • the photoresist material according to this embodiment is crosslinked or converted by baking when irradiated with extreme ultraviolet rays, so that a strong network can be constructed. Therefore, the photoresist material according to this embodiment can prevent evaporation of the photoresist material even when exposed using high-intensity extreme ultraviolet rays such as pulsed extreme ultraviolet rays. Therefore, when exposing using high-intensity pulsed extreme ultraviolet rays, the photoresist material according to this embodiment can shorten the exposure time.
  • the metal oxide precursor preferably contains any one of titanium, zirconium, and hafnium.
  • a resist pattern of ceramics made of metal oxide can be obtained by exposure using extreme ultraviolet rays. Therefore, the present photoresist material can provide a photoresist material with high dry etching resistance.
  • the metal oxide precursor should contain hafnium because the larger the radiation absorption cross section, the higher the sensitivity to the electron beam or EUV light. is more preferable.
  • An example of the metal oxide precursor is shown in the following general formula (III). Note that in formula (III), MO x means a metal oxide.
  • the metal oxide precursor can be obtained by a known production method. For example, it can be obtained by stirring and reacting a metal alkoxide and methyl methacrylate in a suitable organic solvent.
  • examples of the metal alkoxide include titanium (IV) tetraisoprooxide, zirconium (IV) tetraisoprooxide, and hafnium (IV) tetraisoprooxide.
  • the film thickness of the photoresist material is 5 nm or more and 120 nm or more from the viewpoint of forming a high-definition resist pattern and suppressing collapse of the resist pattern. It is preferable that it is below.
  • a resist pattern produced using a photoresist material containing a metal oxide precursor according to one embodiment of the present invention can be used as a dielectric film for a high refractive lens or a waveguide of a millimeter wave device.
  • the photoresist material according to one embodiment of the present invention may contain other components as necessary in addition to the polymer alloy or the metal oxide precursor.
  • other components include antioxidants, photoacid generators, surfactants, amines, dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, and light absorbers.
  • the photoresist material according to one embodiment of the present invention can be manufactured by dissolving a polymer alloy or a metal oxide precursor and, if necessary, other components in an organic solvent component.
  • Any organic solvent may be used as long as it can dissolve each component to be used and form a uniform solution, and any organic solvent may be selected as appropriate from those conventionally known as solvents for photoresist materials. be able to. Examples include toluene, 1-propanol, alkylene glycol monoalkyl ether carboxylates such as propylene glycol monomethyl ether acetate (PGMEA), and the like.
  • FIG. 1 is a flowchart of a resist pattern manufacturing method M10 according to Embodiment 1 of the present invention.
  • the manufacturing method M10 includes a coating step S11, an exposure step S12, and a developing step S13. According to the manufacturing method M10, since the photoresist material is crosslinked or converted by firing by exposing it to light, a resist pattern made of ceramics can be obtained as a result. According to the present resist material, a photoresist material having high dry etching resistance can be provided.
  • the coating step S11 is a step of coating the substrate with a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganobolosilazane, or a resist material containing a metal oxide precursor.
  • the resist material used in this embodiment is the photoresist described in either Embodiment 1 or Embodiment 2. Therefore, in this embodiment, description regarding the photoresist will be omitted.
  • the resist material can be applied onto the substrate by a known method. For example, it can be applied by spin coating, spraying, drop casting, or the like. Of the pair of main surfaces of the substrate, at least the main surface to which the resist material is applied is preferably flat. However, the smoothness of the main surface of the substrate is not particularly limited. Furthermore, the material constituting the substrate is not limited. Examples of materials constituting the substrate include insulators such as quartz and sapphire, semiconductors such as silicon and gallium arsenide, and metals such as aluminum and copper.
  • the exposure step S12 is a step in which the resist material is exposed using extreme ultraviolet rays or electron beams.
  • extreme ultraviolet light including pulsed extreme ultraviolet light
  • a desired pattern is transferred to the resist material by stacking a photomask in close proximity to the resist material applied in the coating step S11.
  • the photomask is not particularly limited as long as it has a desired pattern formed by regions that transmit extreme ultraviolet rays and regions that block extreme ultraviolet rays.
  • a desired pattern is drawn on the resist material by scanning the electron beam.
  • extremely short ultraviolet rays and electron beams are collectively referred to as radiation unless they need to be particularly distinguished.
  • the radiation used in the exposure step S12 may be any radiation that causes a chemical reaction in the resist material, and examples thereof include electron beams, ultraviolet rays, extreme ultraviolet rays, and the like.
  • An example of a chemical reaction is a photoreaction.
  • the form of the chemical reaction is not limited to this.
  • Examples of extreme ultraviolet rays include continuous wave extreme ultraviolet rays whose intensity does not change over time and pulsed extreme ultraviolet rays.
  • the light used in the exposure step S12 is preferably extreme ultraviolet light, and among extreme ultraviolet light, pulsed extreme ultraviolet light is more preferable. By using extreme ultraviolet rays, a pattern with higher definition can be obtained in a shorter exposure time than when using ultraviolet rays.
  • the radiation used in the exposure step S12 can be irradiated with a normal irradiation device used in the technical field.
  • the exposure amount or irradiation amount in the exposure step S12 may be an exposure amount or irradiation amount that causes at least a chemical reaction of crosslinking in the resist material.
  • the intensity of the pulsed extreme ultraviolet rays is preferably 10 9 W/cm 2 or more and 10 14 W/cm 2 or less.
  • the exposure amount or irradiation amount in the exposure step S12 may be adjusted as appropriate by the exposure time, the number of pulses, or attenuation by the metal filter.
  • the exposure amount or irradiation amount may be an exposure amount or irradiation amount that causes firing conversion in addition to crosslinking in the resist material. According to this configuration, a fired resist pattern can be obtained by simply performing the exposure step S12. Therefore, a resist pattern having higher dry etching resistance than a resist pattern made of a crosslinked resist material can be obtained.
  • the developing step S13 is a step of developing the resist pattern by immersing the exposed resist material in a developer.
  • the developer used for development can be appropriately determined depending on the resist material. For example, when the resist material includes a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane, toluene is suitable as the developer. Further, for example, when the resist material contains a metal oxide precursor, cyclohexanone is suitable as the developer.
  • the exposure step S12 may include a first exposure step of exposing the resist material using extreme ultraviolet rays, and a second exposure step.
  • the amount of exposure of extreme ultraviolet rays irradiated to the resist material in the second exposure step is determined to exceed the amount of exposure of extreme ultraviolet rays irradiated to the resist material in the first exposure step.
  • the amount of exposure to extreme ultraviolet rays in the first exposure step is preferably such that a crosslinking photoreaction proceeds in the resist material.
  • the exposure amount of extreme ultraviolet rays in the second exposure step is an exposure amount that converts the resist material into baking.
  • the resist material can be crosslinked in the first exposure step, and the resist material can be baked and converted in the second exposure step. I can do it. Therefore, a resist pattern made of ceramic can be obtained by firing and converting the resist material using only the exposure step S12 using extreme ultraviolet rays. In other words, a resist pattern made of ceramic can be obtained without performing a firing process using a furnace. Therefore, a resist pattern with improved dry etching resistance can be obtained in a short time.
  • the second exposure process uses high-intensity extreme ultraviolet rays. Therefore, it is preferable to use pulsed extreme ultraviolet rays in the second exposure step. Note that when pulsed extreme ultraviolet rays are used in the second exposure step, it is preferable to use pulsed extreme ultraviolet rays also in the first exposure step.
  • FIG. 1 is a flowchart of a resist pattern manufacturing method M20 according to Embodiment 1 of the present invention.
  • the manufacturing method M20 includes a coating step S21, an exposure step S22, a developing step S23, and a baking step S24.
  • Each of the coating process S21, the exposure process S22, and the developing process S23 is the same as each of the coating process S11, the exposure process S12, and the developing process S13 in the manufacturing method M10. Therefore, in this embodiment, descriptions of the coating process S21, the exposure process S22, and the developing process S23 are omitted. Note that the exposure amount or irradiation amount in the exposure step S22 is determined so that the crosslinking photoreaction proceeds in the resist material.
  • the baking step S24 is a step carried out after the developing step S23, and is a step of converting the developed resist material into baking to obtain a layered member made of an insulator or semiconductor to which the pattern of the photomask has been transferred. be.
  • an electric furnace is used to bake the developed resist material.
  • the firing step S24 is performed after the exposure step S22, so the resist material can be reliably turned into ceramic. Therefore, it is possible to reduce the non-ceramic components that may be contained in the obtained resist pattern, so that the dry etching resistance of the resist pattern can be further improved. Further, when using a resist material containing a metal oxide precursor, the film density of the pattern can be improved without changing the state of the metal oxide due to baking, so that etching resistance can be improved. Furthermore, since excess organic matter can be removed by firing, the generation of outgas can be significantly suppressed.
  • Baking conversion can be performed by heating the developed resist material. Heating is not particularly limited, but from the viewpoint of preventing oxidation, it is preferable to perform the heating in a vacuum or under an argon atmosphere. From the viewpoint of thermal decomposition and calcination conversion temperature, the heating temperature is preferably 400°C or higher, more preferably 600°C or higher, and particularly preferably 800°C or higher. Further, from the viewpoint of protecting the substrates, it is preferable that the melting point of each substrate is 100° C. or lower. The density of ceramics can be adjusted as appropriate by adjusting the heating time. When heating at 400°C or higher, heating is preferably at least 10 hours; when heating at 600°C or higher, heating is preferably at least 5 hours; when heating at 800°C or higher, heating is preferably at least 2 hours. .
  • the method for manufacturing a resist pattern according to one aspect of the present invention may include steps other than the steps shown in Embodiments 1 and 2.
  • Other processes include, for example, a wet etching process, a dry etching process, and the like. Other steps can be performed using known methods.
  • FIG. 3 is a perspective view of the resist pattern 1.
  • the resist pattern 1 is an amorphous film made of silicon carbide and is two-dimensionally patterned.
  • the resist pattern 1 may be an amorphous film made of at least one of silicon carbide, silicon dioxide, silicon nitride, and borosilicon carbonitride. According to such a configuration, the ceramic insulating film can be formed using lithography technology.
  • the resist pattern 1 includes a substrate 10 and a resist 11.
  • the resist 11 is directly formed on one main surface (the upper main surface in FIG. 3) of the substrate 10.
  • one or more other layers for example, a metal layer, a semiconductor layer, etc.
  • one or more other layers for example, a metal layer, a semiconductor layer, etc.
  • Resist 11 is made of silicon carbide.
  • the resist 11 can be produced by using a polymer alloy containing at least polycarbosilane among the polymer alloys described in [Photoresist Material].
  • the resist 11 may be made of at least one of silicon carbide, silicon dioxide, silicon nitride, and borosilicon carbonitride.
  • the resist 11 can be produced by using at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane among the polymer alloys described in [Photoresist material].
  • the substrate 10 is the same as the substrate used in the manufacturing method M10 shown in FIG. Therefore, in this embodiment, description of the substrate 10 is omitted.
  • the resist pattern 1 can be manufactured by using the resist material described in Embodiment 1 and implementing the manufacturing method M10 shown in FIG. 1 or the manufacturing method M20 shown in FIG. 2. Therefore, in this embodiment, description of the resist 11 is omitted.
  • Example 2 A sample for irradiation with a film thickness of about 200 nm was obtained by performing the same operation as in Example 1, except that the amount of allylhydridopolycarbosilane added was changed to 5 wt%.
  • Example 3 A metal alkoxide (titanium (IV) tetraisoprooxide) was reacted with methyl methacrylate in a 1-propanol solution with stirring at room temperature for 1 hour to prepare a metal oxide precursor. Next, a sample for irradiation with a film thickness of about 80 nm was prepared by spin coating on a silicon wafer.
  • Example 4 A sample for irradiation with a film thickness of about 80 nm was prepared in the same manner as in Example 3 except that zirconium (IV) tetraisoprooxide was used as the metal alkoxide.
  • Example 5 A sample for irradiation with a film thickness of about 80 nm was prepared in the same manner as in Example 3 except that hafnium (IV) tetraisoprooxide was used as the metal alkoxide.
  • Comparative example 2 A sample for irradiation with a film thickness of about 200 nm was obtained in the same manner as in Comparative Example 1 except that ZEP520A (manufactured by Nippon Zeon Co., Ltd.) was used as the resist polymer.
  • ZEP520A manufactured by Nippon Zeon Co., Ltd.
  • Comparative example 3 A sample for irradiation with a film thickness of about 200 nm was obtained in the same manner as in Comparative Example 1 except that UVIII (manufactured by ROHM and HRRS) was used as the resist polymer.
  • Comparative example 4 A sample for irradiation with a film thickness of about 200 nm was obtained in the same manner as in Comparative Example 1 except that PHS (polyhydroxystyrene, Mw ⁇ 15,000, manufactured by Aldrich) was used as the resist polymer.
  • PHS polyhydroxystyrene, Mw ⁇ 15,000, manufactured by Aldrich
  • EB-ENGINE electron beam irradiation device
  • Scan irradiation was applied to a 1 cm square area of each sample so that the absorbed dose was 100 ⁇ C/cm 2 to 600 ⁇ C/cm 2 .
  • EUV Extreme ultraviolet
  • EUV exposure device ENERGETIQ, EQ-10, Electrodeless Z-Pinch TM , 10Watt
  • the sample was spot irradiated.
  • Pulsed EUV irradiation Pulsed EUV (1 to 17 nJ/pulse) with a spot size of about 7 ⁇ m was irradiated using a pulsed EUV irradiation device manufactured by the Kansai Photon Science Institute of the Quantum Science and Technology Research and Development Organization (QST). In addition, pulsed EUV (1 to 17 nJ/pulse) with a spot size of approximately 7 ⁇ m was irradiated at the X-ray free electron laser facility SACLA of the Synchrotron Radiation Research Center.
  • QST Quantum Science and Technology Research and Development Organization
  • FIG. 5 shows the results of Examples 3 to 5 in which EB or EUV irradiation was performed.
  • (a) is the sensitivity curve of Example 3 subjected to EB irradiation
  • (b) is the sensitivity curve of Example 4 subjected to EB irradiation
  • (c) is the sensitivity curve of Example 5 subjected to EB irradiation
  • ( d) shows the sensitivity curve of Example 3 with EUV irradiation
  • (e) shows the sensitivity curve of Example 4 with EUV irradiation
  • (f) shows the sensitivity curve of Example 5 with EUV irradiation.
  • the vertical axis indicates the standardized film thickness (nm)
  • the horizontal axis indicates the irradiation amount or exposure amount ( ⁇ C/cm 2 or mJ/cm 2 ).
  • FIG. 6 shows the appearance of the resist films of Examples 2 and 3 and Comparative Example 1 before and after the baking conversion.
  • (a) shows the state of the resist film of Example 2 before and after the baking conversion
  • (b) shows the state of the resist film of Example 3 before and after the baking conversion
  • (c) shows the state of the resist film of Example 3 before and after the baking conversion.
  • the state of the resist film of Comparative Example 1 before and after conversion is shown.
  • FIG. 6 if the shape (square) of the resist film before firing conversion remains after firing conversion, it can be determined that the resist pattern remains.
  • Examples 2 and 3 exhibited high heat resistance, and it was confirmed that the pattern remained even after the firing conversion. On the other hand, in Comparative Example 1, evaporation occurred due to thermal decomposition, and no resist pattern remained. In Comparative Examples 2 and 3 as well, evaporation due to thermal decomposition occurred and no resist pattern remained.
  • Example 2 and Comparative Example 1 The etching resistance of Example 2 and Comparative Example 1 is shown in FIG. 7, and the etching resistance of Example 3 and Comparative Examples 1 to 4 is shown in FIG. 8(a). is shown in FIG. 8(b), and the etching resistance of Example 5 and Comparative Examples 1 to 4 is shown in FIG. 8(c).
  • the vertical axis shows the film thickness (nm) after etching
  • the horizontal axis shows the etching time (seconds).
  • approximate curves are shown in which the intercept of each etching time with respect to the film thickness is set to 0 for developed Examples 3 to 5, baked-converted Examples 3 to 5, and Comparative Example 1.
  • Example 2 As shown in FIG. 7, when the etching resistance of Example 2 was compared with Comparative Example 1, it was found that the etching resistance was significantly improved. In addition, it was found that Example 2, which underwent firing conversion, had further improved etching resistance.
  • the photoresist material of the present invention has sufficient pattern forming ability even with a pulsed EUV light source.
  • Resist patterns produced using Examples 2 and 5 by irradiation with EUV (wavelength: 13.5 nm) light derived from a free electron laser are shown in FIGS. 9 and 10, respectively.
  • the photoresist material according to aspect 1 of the present invention is a photoresist material for extreme ultraviolet lithography, and is a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane, or , including metal alkoxides.
  • the photoresist material configured as described above is crosslinked or converted by firing by being irradiated with extreme ultraviolet rays, and as a result, a resist pattern made of ceramics can be obtained. According to the present resist material, a photoresist material having high dry etching resistance can be provided.
  • the photoresist material according to aspect 2 of the present invention in addition to the configuration of the photoresist material according to aspect 1, a configuration including a polymer alloy containing polycarbosilane and allylhydridopolycarbosilane is adopted. .
  • An example of a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganoborosilazane includes a polymer alloy containing polycarbosilane and allylhydridopolycarbosilane. According to the above configuration, a ceramic resist pattern made of silicon carbide can be obtained by exposure using extreme ultraviolet rays. Therefore, the present photoresist material can provide a photoresist material with high dry etching resistance.
  • the ratio of allylhydridopolycarbosilane to polycarbosilane is 0.1 wt% or more and 50 wt% or less. configuration has been adopted.
  • the metal alkoxide contains any one of titanium, zirconium, and hafnium.
  • the metal alkoxide preferably contains any one of titanium, zirconium, and hafnium. According to the above configuration, a resist pattern of ceramics made of metal oxide can be obtained by exposure using extreme ultraviolet rays. Therefore, the present photoresist material can provide a photoresist material with high dry etching resistance.
  • a method for manufacturing a resist pattern according to aspect 5 of the present invention is to apply a resist material containing a polymer alloy containing at least one of polycarbosilane, polysiloxane, polysilazane, and polyorganobolosilazane or a metal alkoxide onto a substrate.
  • an exposure step of bringing a photomask close to a substrate coated with the resist material to expose the resist material and a developing step of developing the exposed resist material.
  • the resist material configured as described above is crosslinked or fired by being exposed to light, and becomes a two-dimensional pattern of ceramics.
  • a resist pattern made of ceramics can be obtained. Therefore, a photoresist pattern having high dry etching resistance can be provided.
  • a baking step performed after the developing step in which the developed resist material is A configuration is adopted which further includes a firing step of obtaining a layered member made of an insulator or semiconductor onto which the pattern of the photomask is transferred by performing firing conversion.
  • the resist pattern can be reliably made into ceramic. Therefore, the dry etching resistance of the obtained resist pattern can be further improved.
  • the light used in the exposure step is extreme ultraviolet rays.
  • the present manufacturing method produces the same effects as the photoresist material according to Aspect 1 described above. Further, according to the present manufacturing method, a pattern with higher definition can be obtained in a shorter exposure time than when exposing using ultraviolet rays.
  • the exposure step includes a first exposure step of exposing the resist material using extreme ultraviolet rays. and a second exposure step, and the amount of exposure of the extreme ultraviolet rays irradiated to the resist material in the second exposure step is equal to the amount of exposure of the extreme ultraviolet rays irradiated to the resist material in the first exposure step. exceed.
  • the resist pattern according to aspect 9 of the present invention is an amorphous film made of at least one of silicon carbide, silicon dioxide, silicon nitride, and borosilicon carbonitride, and is a two-dimensionally patterned amorphous film. Consisting of
  • the ceramic insulating film can be formed using lithography technology.
  • Resist pattern 10 Substrate 11 Resist M10 Resist pattern manufacturing method M20 Resist pattern manufacturing method S11 Coating process S12 Exposure process S13 Developing process S21 Coating process S22 Exposure process S23 Developing process S24 Baking process

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
PCT/JP2023/009016 2022-04-15 2023-03-09 レジスト材料、レジストパターンの製造方法、及び、レジストパターン WO2023199659A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-067860 2022-04-15
JP2022067860 2022-04-15

Publications (1)

Publication Number Publication Date
WO2023199659A1 true WO2023199659A1 (ja) 2023-10-19

Family

ID=88329334

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/009016 WO2023199659A1 (ja) 2022-04-15 2023-03-09 レジスト材料、レジストパターンの製造方法、及び、レジストパターン

Country Status (2)

Country Link
TW (1) TW202349115A (zh)
WO (1) WO2023199659A1 (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08115863A (ja) * 1994-10-13 1996-05-07 Yamaha Corp 半導体デバイス
JPH11288087A (ja) * 1998-04-03 1999-10-19 Hitachi Chem Co Ltd 感光性樹脂組成物
JP2003277612A (ja) * 2002-03-20 2003-10-02 Osaka Gas Co Ltd ポリマー組成物およびパターン形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08115863A (ja) * 1994-10-13 1996-05-07 Yamaha Corp 半導体デバイス
JPH11288087A (ja) * 1998-04-03 1999-10-19 Hitachi Chem Co Ltd 感光性樹脂組成物
JP2003277612A (ja) * 2002-03-20 2003-10-02 Osaka Gas Co Ltd ポリマー組成物およびパターン形成方法

Also Published As

Publication number Publication date
TW202349115A (zh) 2023-12-16

Similar Documents

Publication Publication Date Title
JP5300799B2 (ja) パターン形成方法及びポリマーアロイ下地材料
JP5318217B2 (ja) パターン形成方法
US6753129B2 (en) Method and apparatus for modification of chemically amplified photoresist by electron beam exposure
JP4852360B2 (ja) 多層リソグラフィプロセスにおいて用いられる複素環芳香族構造物を含む基層組成物、リソグラフィ構造物、材料層または材料要素を基板上に形成させる方法
TWI361333B (en) Photoresist composition
JP2005070776A (ja) 反射防止ハードマスク組成物とそれを用いた半導体デバイスの製造方法
TW201030804A (en) A hardmask process for forming a reverse tone image using polysilazane
TW201005036A (en) Aqueous curable imprintable medium and patterned layer forming method
TW201718676A (zh) 新穎嵌段共聚物之組合物及自我組裝方法
US20060166132A1 (en) Ultraviolet light transparent nanoparticles for photoresists
CN112462572B (zh) 光刻胶、光刻胶的图案化方法及生成印刷电路板的方法
TWI754661B (zh) 用於自組裝應用之聚合物組合物
JP2022541818A (ja) 有機金属の金属カルコゲナイドクラスター及びリソグラフィへの応用
KR102538628B1 (ko) 무기 포토레지스트 조성물 및 포토리소그래피 공정
CN111965947B (zh) 光刻胶、光刻胶的图案化方法及集成电路板的刻蚀方法
WO2023199659A1 (ja) レジスト材料、レジストパターンの製造方法、及び、レジストパターン
KR100500453B1 (ko) 이중층 레지스트막의 하부 레지스트 층의 형성방법
JP3503976B2 (ja) パターン形成方法
EP1176468A1 (fr) Résine, bi-couche de résine pour photolithographie dans l'extrême ultraviolet (EUV) et procédé de photolithogravure en extrême ultraviolet (EUV)
JP2675162B2 (ja) 感光性樹脂組成物およびこれを用いたパターン形成方法
TW200807500A (en) Forming method of resist pattern and writing method using electric charge corpuscular ray
TWI845539B (zh) 氫矽酸鹽樹脂塗佈組成物、產生組成物的方法、基板圖案化的方法、形成抗蝕膜的方法以及產生半導體裝置的方法
US6989227B2 (en) E-beam curable resist and process for e-beam curing the resist
JP3957533B2 (ja) レジスト材料及びレジストパターン形成方法
US8512937B2 (en) Lithographic dry development using optical absorption

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23788081

Country of ref document: EP

Kind code of ref document: A1