WO2022176833A1 - Pellicule et procédé de fabrication de pellicule - Google Patents

Pellicule et procédé de fabrication de pellicule Download PDF

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Publication number
WO2022176833A1
WO2022176833A1 PCT/JP2022/005846 JP2022005846W WO2022176833A1 WO 2022176833 A1 WO2022176833 A1 WO 2022176833A1 JP 2022005846 W JP2022005846 W JP 2022005846W WO 2022176833 A1 WO2022176833 A1 WO 2022176833A1
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Prior art keywords
pellicle
substrate
pellicle film
film
layer
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PCT/JP2022/005846
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English (en)
Japanese (ja)
Inventor
秀彦 奥
康大 野村
一郎 秀
啓介 川村
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エア・ウォーター株式会社
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Publication of WO2022176833A1 publication Critical patent/WO2022176833A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/06—Heating of the deposition chamber, the substrate or the materials to be evaporated
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • G03F1/64—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof characterised by the frames, e.g. structure or material, including bonding means therefor

Definitions

  • the present invention relates to a pellicle and a method for manufacturing a pellicle. More specifically, the present invention relates to a pellicle and a method for manufacturing a pellicle that can prevent cracking of the pellicle film.
  • a resist is applied to a semiconductor wafer, and the necessary portions of the applied resist are irradiated with exposure light using a photomask to obtain the desired pattern on the semiconductor wafer.
  • a resist pattern having a regular shape is produced.
  • the photomask is covered with a dust-proof cover called a pellicle to prevent foreign matter from adhering to the photomask.
  • a pellicle film of the pellicle a material having high exposure light transmittance and high resistance to exposure light (low deterioration and deformation at high temperatures) is suitable, and Si (silicon) is used.
  • an organic thin film is used as the pellicle film.
  • the wavelength of the exposure light becomes short, such as EUV light
  • the energy received by the pellicle film from the exposure light increases.
  • inorganic thin films include Si, SiN (silicon nitride), C (carbon) (graphite, graphene, diamond-like carbon (DLC), amorphous carbon, etc.), SiC (silicon carbide), and the like.
  • Patent Document 1 listed below discloses a method of manufacturing a compound semiconductor substrate, which includes the steps of forming a SiC film on the surface of a Si substrate and removing at least part of the back surface of the Si substrate by wet etching. . In the step of removing at least part of the back surface of the Si substrate, the Si substrate and the SiC film are moved relative to the chemical used for wet etching.
  • Patent Document 2 discloses a pellicle that includes a pellicle membrane and a support member that supports the pellicle membrane.
  • the pellicle film is made of DLC, amorphous carbon, graphite, silicon carbide, or the like.
  • the pellicle frame is made of silicon, metal, or the like.
  • the pellicle is manufactured by etching a substrate to shape it into a support material and forming a pellicle film on the substrate.
  • the Young's modulus in the ⁇ 110> direction of a P + -type Si thin film crystal layer implanted with a high concentration of B (boron) using a thermal diffusion method is It is disclosed to be 26% to 28% lower than the ⁇ 110>Young's modulus of the thin film crystal layer.
  • the problem that cracks are likely to occur in the pellicle film when the pellicle film is thinned is not limited to the case where the pellicle film is made of SiC, but is a problem that occurs in any pellicle film.
  • the problem that the pellicle film tends to crack when the pellicle film is thinned may be caused by the stress received from the border (support) having an arbitrary shape.
  • the present invention is intended to solve the above problems, and its object is to provide a pellicle and a pellicle manufacturing method that can prevent cracking of the pellicle film.
  • a pellicle according to one aspect of the present invention includes a border including a B-containing Si layer, and a pellicle film formed on one main surface side of the Si layer.
  • the resistivity of the Si layer is preferably greater than 0 and 0.02 ⁇ cm or less.
  • the pellicle film preferably has a thickness of 10 nm or more and 50 nm or less.
  • the pellicle film is in contact with one main surface of the Si layer and is epitaxially grown on the one main surface side of the Si layer.
  • the pellicle preferably further comprises an adhesive film that bonds the pellicle film and the Si layer.
  • the pellicle film is preferably made of SiC.
  • the boater preferably includes a through hole, and the pellicle membrane is exposed on the bottom surface of the through hole.
  • a pellicle manufacturing method includes the steps of preparing a B-containing Si layer and forming a pellicle film on one main surface side of the Si layer.
  • the above manufacturing method preferably further comprises a step of forming a border including the Si layer by forming a through hole in the Si layer, and the pellicle film is exposed on the bottom surface of the through hole.
  • the step of forming the border includes a step of removing part of the Si layer by wet etching, and in the step of removing part of the Si layer by wet etching, to move the Si layer and the pellicle film relatively.
  • the step of forming the border further includes the step of forming a recess having a bottom surface made of Si in the other main surface of the Si layer, and the step of removing part of the Si layer by wet etching, Wet etching is performed on the Si existing on the bottom surface of the recess.
  • the resistivity of the Si layer is preferably greater than 0 and 0.02 ⁇ cm or less.
  • the pellicle film preferably has a thickness of 10 nm or more and 50 nm or less.
  • the step of forming the pellicle film includes the step of epitaxially growing the pellicle film in contact with one main surface of the Si layer.
  • the step of forming the pellicle film includes a step of adhering the border and the pellicle film with an adhesive.
  • the pellicle film is preferably made of SiC.
  • FIG. 1 is a cross-sectional view showing a configuration of a pellicle 1 according to a first embodiment of the invention
  • FIG. FIG. 4 is a cross-sectional view showing a configuration of a modification of the pellicle 1 according to the first embodiment of the present invention
  • FIG. 2 is a plan view showing the configuration of the pellicle 1 when viewed from a direction perpendicular to the surface 12a of the pellicle film 12 in the first embodiment of the present invention
  • FIG. 4 is a cross-sectional view showing the first step of the method of manufacturing the pellicle 1 according to the first embodiment of the invention
  • FIG. 4 is a cross-sectional view showing a second step of the method of manufacturing the pellicle 1 according to the first embodiment of the invention
  • FIG. 6 is a cross-sectional view showing a first step of a modified example of the steps shown in FIG. 5
  • FIG. 6 is a cross-sectional view showing a second step of a modified example of the steps shown in FIG. 5
  • FIG. 4 is a cross-sectional view showing a third step of the method for manufacturing the pellicle 1 according to the first embodiment of the invention
  • FIG. 4 is a cross-sectional view showing a fourth step of the method for manufacturing the pellicle 1 according to the first embodiment of the invention
  • FIG. 10 is a cross-sectional view showing a fifth step of the method for manufacturing the pellicle 1 according to the first embodiment of the invention
  • FIG. 4 is a diagram schematically showing a first method of wet etching Si according to the first embodiment of the present invention
  • FIG. 4 is a diagram schematically showing a second method of wet etching Si according to the first embodiment of the present invention
  • It is a figure which shows typically the 3rd method of the wet etching of Si in the 1st Embodiment of this invention.
  • FIG. 2 is an enlarged view of part A in the pellicle 1 shown in FIG. 1; It is a figure explaining the effect of the 1st Embodiment of this invention.
  • FIG. 4 is a cross-sectional view showing the configuration of a pellicle 1 according to a second embodiment of the invention
  • FIG. 10 is a cross-sectional view showing the first step of the method of manufacturing the pellicle 1 according to the second embodiment of the present invention
  • FIG. 10 is a cross-sectional view showing a second step of the method for manufacturing the pellicle 1 according to the second embodiment of the invention
  • FIG. 10 is a cross-sectional view showing a third step of the method for manufacturing the pellicle 1 according to the second embodiment of the invention
  • FIG. 10 is a cross-sectional view showing a fourth step of the method for manufacturing the pellicle 1 according to the second embodiment of the invention
  • FIG. 10 is a cross-sectional view showing a fifth step of the method for manufacturing the pellicle 1 according to the second embodiment of the invention
  • FIG. 4 is a diagram showing the yield rate of each of samples A to D in one example of the present invention
  • a pellicle 1 (an example of a pellicle) in the present embodiment includes a Si border (support) 11 (an example of a border) and a pellicle film 12 (an example of a pellicle film).
  • the Si border 11 has an annular planar shape surrounding the through hole 13 (an example of a through hole).
  • the Si border 11 includes a front surface 11a, a back surface 11b, and side surfaces 11c.
  • the Si border 11 is a border including the Si layer 113 .
  • the Si border 11 consists of the Si layer 113 .
  • the (100) plane of Si is exposed on the surface 11 a of the Si border 11 .
  • the (111) plane of the Si layer 113 or the (110) plane of Si may be exposed on the surface 11a of the Si border 11 .
  • the Si layer 113 contains B.
  • the concentration of B in the Si layer 113 is preferably as high as possible so that B does not precipitate in the Si crystal.
  • the Si layer 113 has P-type conductivity due to the action of B in the Si layer 113 .
  • the Si layer 113 has a resistivity of greater than 0 and 0.02 ⁇ cm or less, preferably 0.005 ⁇ cm or less.
  • the pellicle film 12 is made of SiC and formed on the surface 113 a of the Si layer 113 .
  • a pellicle membrane 12 is supported by the Si border 11 .
  • the pellicle film 12 includes a front surface 12a, a back surface 12b, and side surfaces 12c. A central portion of the back surface 12 b of the pellicle film 12 is exposed at the bottom of the through-hole 13 .
  • the pellicle film 12 is not formed on the back surface 11b of the Si border 11, and the back surface 11b of the Si border 11 is exposed.
  • the pellicle film 12 has a thickness w of 10 nm or more and 10 ⁇ m or less.
  • the thickness w is preferably 1 ⁇ m or less, more preferably 500 nm or less, most preferably 50 nm or less. As the thickness w of the pellicle film 12 decreases, the transmittance of the pellicle film 12 improves, but the mechanical strength of the pellicle film 12 decreases.
  • the pellicle film 12 in the present embodiment is epitaxially grown on the surface 113a of the Si layer 113 (the surface 11a of the border 11).
  • the structure of the SiC crystals in the pellicle film 12 in contact with the surface 113a of the Si layer 113 is influenced by the Si crystals in the Si layer 113, and is different from the bulk SiC crystal structure.
  • there is Pellicle film 12 is in contact with surface 113 a of Si layer 113 .
  • the pellicle film 12 is made of single crystal 3C-SiC, polycrystal 3C-SiC, amorphous SiC, or the like. In particular, when the pellicle film 12 is epitaxially grown on the surface of the Si layer 113, the pellicle film 12 is generally made of 3C--SiC.
  • the border only needs to include a Si layer, and may further include a film made of another material such as a SiO 2 (silicon oxide) film or a SiN film (silicon nitride).
  • the border may also include a sapphire substrate and a Si layer formed on the sapphire substrate.
  • FIG. 2 is a cross-sectional view showing a configuration of a modification of the pellicle 1 according to the first embodiment of the invention. 2 is a cross-sectional view taken along a plane perpendicular to the surface 12a of the pellicle film 12.
  • FIG. 2 is a cross-sectional view showing a configuration of a modification of the pellicle 1 according to the first embodiment of the invention. 2 is a cross-sectional view taken along a plane perpendicular to the surface 12a of the pellicle film 12.
  • a Si border 11 made of an SOI (Silicon On Insulator) substrate is used.
  • the Si border 11 of this modified example is a border including a Si substrate 111 , a SiO 2 film 112 and a Si layer 113 .
  • a SiO 2 film 112 is formed on the surface of the Si substrate 111 .
  • the Si layer 113 is formed on the surface of the SiO 2 film 112 .
  • the thickness of the Si layer 113 is preferably 5 nm or more and 100 ⁇ m or less.
  • the pellicle film 12 in this modified example is also epitaxially grown on the surface 113a of the Si layer 113 (the surface 11a of the border 11).
  • the structure of the SiC crystals in the pellicle film 12 in contact with the surface 113a of the Si layer 113 is influenced by the Si crystals in the Si layer 113, and is different from the bulk SiC crystal structure.
  • there is Pellicle film 12 is in contact with surface 113 a of Si layer 113 .
  • the border is the Si border 11 made of the Si layer 113 .
  • the border may be understood by replacing the SOI substrate as in the modified example with the Si border 11 or the like.
  • FIG. 3 is a plan view showing the configuration of the pellicle 1 when viewed from a direction perpendicular to the surface 12a of the pellicle film 12 in the first embodiment of the invention.
  • the Si border 11 is indicated by a dotted line for the purpose of showing the shape of the Si border 11, but in reality the Si border 11 cannot be seen directly.
  • each of Si border 11, pellicle film 12, and through-hole 13 has an arbitrary planar shape.
  • the pellicle film 12 has its outer periphery supported by an annular Si border 11 .
  • the mechanical strength of the pellicle film 12 is reinforced by the Si border 11 .
  • Each of the Si border 11, the pellicle film 12, and the through-hole 13 may have a circular planar shape, for example, as shown in FIG. It may have a rectangular planar shape.
  • the Si border 11 has a quadrangular annular planar shape.
  • each of the Si border 11 and the pellicle film 12 may have a circular planar shape, and the through hole 13 may have a rectangular planar shape.
  • the size of the through-hole 13 is arbitrary and may be determined according to the mechanical strength required for the pellicle 1 and the like.
  • FIG. 1 a method for manufacturing the pellicle 1 according to the present embodiment will be described with reference to FIGS. 4 to 10.
  • a disk-shaped Si substrate 113 (with no through-holes 13 formed therein) is prepared.
  • the Si substrate 113 is a substrate from which the Si layer 113 in FIG. 1 is formed, and contains boron.
  • Si in the central portion RG1 of the rear surface 113b of the Si substrate 113 is removed.
  • the removal of Si in central portion RG1 may be performed by mechanically grinding Si in central portion RG1 of Si substrate 113 .
  • the removal of Si in the central portion RG1 is performed by forming a photoresist in a region of the rear surface 113b of the Si substrate 113 excluding the central portion RG1 and etching the Si in the central portion RG1 using the formed photoresist as a mask.
  • removal of Si from the central portion RG1 may be performed by the following method.
  • a mask layer 14 made of a silicon oxide film or a silicon nitride film is formed on the entire rear surface 113b of the Si substrate 113 . Subsequently, a photoresist 15 patterned into a required shape is formed on the back surface of the mask layer 14 .
  • mask layer 14 is patterned by wet etching using photoresist 15 as a mask. As a result, only the outer peripheral portion of the mask layer 14 is left.
  • a hydrofluoric acid solution or the like is used as a chemical solution for wet etching the mask layer 14 .
  • a phosphoric acid solution or the like is used as a chemical solution for wet etching the mask layer 14 .
  • Si in the central portion RG1 is removed by wet etching using a chemical solution such as a mixed acid. After that, the photoresist 15 and the mask layer 14 are removed.
  • the photoresist 15 may be removed before the wet etching of Si.
  • the process of forming the mask layer 14 shown in FIG. 6 may be omitted by preparing a substrate in which the mask layer 14 is formed on the rear surface 113b of the Si substrate 113 in advance.
  • a silicon oxide film and an oxide film or a nitride film other than the silicon oxide film may be used.
  • recess 16 is formed in rear surface 113b of Si substrate 113. As shown in FIG. The recess 16 has a depth that does not penetrate the Si substrate 113 , and the bottom surface of the recess 16 is made of Si of the Si substrate 113 . Due to the presence of the concave portion 16, the thickness of the central portion of the Si substrate 113 (length in the vertical direction in FIG. 8) is thinner than the thickness of the outer peripheral portion of the Si substrate 113. FIG.
  • the pellicle film 12 is formed on the surface 113a of the Si substrate 113.
  • the pellicle film 12 in contact with the surface 113a of the Si substrate 113 is epitaxially grown.
  • the pellicle film 12 is formed, for example, on an underlying layer made of SiC obtained by carbonizing the surface 113a of the Si substrate 113, using an MBE (Molecular Beam Epitaxy) method, a CVD (Chemical Vapor Deposition) method, or the like. filmed.
  • the pellicle film 12 may be formed on the surface 113a of the Si substrate 113 using the MBE method, the CVD method, or the like.
  • the pellicle film 12 may be formed only by carbonizing the surface 113 a of the Si substrate 113 .
  • the SiC film of the pellicle film 12 may also be formed on the side surface 113 c of the Si substrate 113 .
  • the portion of the Si substrate 113 existing on the bottom surface RG2 of the recess 16 is removed by wet etching.
  • Si of the outer peripheral portion (the portion surrounding the recess 16) RG3 of the back surface 113b of the Si substrate 113 is removed together with the Si of the bottom surface RG2.
  • the recess 16 becomes the through hole 13.
  • a Si substrate 113 is formed into a Si border 11 including through holes 13 .
  • the back surface 12 b of the pellicle film 12 is exposed at the bottom surface of the through hole 13 .
  • Wet etching of Si on the bottom surface RG2 is performed by moving the Si substrate 113 and the pellicle film 12 relative to the chemical used for wet etching.
  • Moving the Si substrate 113 and the pellicle film 12 includes rotating the Si substrate 113 and the pellicle film 12 without changing the positions of the Si substrate 113 and the pellicle film 12, and changing the positions of the Si substrate 113 and the pellicle film 12. (In other words, moving the Si substrate 113 and the pellicle film 12) and rotating the Si substrate 113 and the pellicle film 12 while changing the positions of the Si substrate 113 and the pellicle film 12 are included.
  • a chemical solution used for wet etching of Si for example, a mixed acid containing hydrofluoric acid and nitric acid, a potassium hydroxide (KOH) aqueous solution, or the like is used.
  • an alkaline solution such as an aqueous solution of potassium hydroxide
  • a chemical solution for wet etching of Si even the pellicle film 12 may be etched through pinholes present at low density in the pellicle film 12 .
  • the direction in which the Si substrate 113 and the pellicle film 12 are moved during wet etching of Si is arbitrary. However, in order to avoid the situation where the pellicle film 12 is damaged by the pressure received from the chemical solution while the Si substrate 113 and the pellicle film 12 are being moved, the pellicle film 12 may be prevented from being damaged by the following first to third methods. It is preferable to move the Si substrate 113 and the pellicle film 12 in a direction within a plane (plane PL in FIGS. 11 to 13) parallel to the surface 12a of .
  • 11 to 13 are diagrams schematically showing first to third methods of wet etching of Si according to the first embodiment of the present invention.
  • 11 to 13 the structure immediately before the wet etching of Si is referred to as an intermediate 2.
  • the structure immediately after the process of FIG. 9 corresponds to the intermediate 2
  • the structure immediately after the process of FIG. 20 corresponds to the intermediate 2.
  • the first method is to remove Si by spin etching.
  • the preform 2 is fixed to the fixing table HP so that the rear surface 113b of the Si substrate 113 faces upward.
  • the fixing table HP is rotated around a rotation axis extending in a direction orthogonal to the rear surface 113b.
  • the chemical solution MA etching liquid used for wet etching is injected into the rear surface 113 b of the Si substrate 113 while the intermediate body 2 is rotated without changing the position of the intermediate body 2 .
  • the rotation speed of the fixed base HP is set to, for example, about 500 to 1500 rpm.
  • a plurality of preforms 2 are fixed to a fixing base HP in an upright state. Then, a plurality of intermediates 2 are immersed in the chemical solution MA filled inside the reaction container CS, and the positions of the intermediates 2 are shown by arrows AR2 within a plane PL parallel to the surface 12a of the pellicle film 12. While changing , the intermediate body 2 and the fixed base HP are rotated.
  • the intermediate 2 is fixed to the fixing table HP so that the back surface 113b of the Si substrate 113 faces upward. Then, the intermediate 2 is immersed in the chemical solution MA filled inside the reaction container CS, and the intermediate 2 and the fixing table HP are placed in a plane PL parallel to the surface 12a of the pellicle film 12 as indicated by an arrow AR3. move back and forth in a straight line.
  • FIG. 14 is an enlarged view of part A in the pellicle 1 shown in FIG. In FIG. 14, the amount of change in the width of the Si substrate 113 is emphasized more than the actual one.
  • mixed acid containing hydrofluoric acid and nitric acid has the effect of isotropically etching Si. Therefore, when Si is wet-etched using a mixed acid containing hydrofluoric acid and nitric acid as a chemical, the width d of the Si substrate 113 (the distance between the inner peripheral surface and the outer peripheral surface of the Si substrate 113) is , decreases with increasing distance from the pellicle film 12 (from the pellicle film 12 toward the rear surface 113b of the Si substrate 113).
  • the recess 16 may be formed in the Si substrate 113 after the pellicle film 12 is formed on the surface 113a of the Si substrate 113 .
  • the through holes 13 may be formed only by wet etching of Si without forming the recesses 16 .
  • the pellicle film 12 may be formed by bonding the Si substrate 113 and a bulk SiC substrate and then thinning the SiC substrate.
  • the pellicle film 12 may be formed on the surface 113 a side of the Si substrate 113 , and any film may be formed between the pellicle film 12 and the Si substrate 113 .
  • a film made of a material other than SiC, such as a graphene film, may be formed on the surface 12a of the pellicle film 12.
  • FIG. 15 is a diagram explaining the effects of the first embodiment of the present invention. In addition, in FIG. 15, the deformation of the border 11 is emphasized more than the actual case.
  • the pellicle film 12 receives a tensile stress F1 from the Si border 11, and the Si border 11 receives a compressive stress F2 from the pellicle film 12.
  • the pellicle film 12 has no slack due to the tensile stress F1.
  • the inventors of the present application have found that excessive tensile stress F1 (approximately 300 MPa) applied to the conventional pellicle film 12 from the Si border 11 causes the pellicle film 12 to crack.
  • the inventors of the present application focused on the fact that the Young's modulus of the Si layer decreases as the B concentration in the Si layer increases (see Non-Patent Document 1).
  • the Young's modulus of the Si layer 113 is lower than when the Si layer 113 does not contain B, and the Si border 11 is compressed. It becomes easy to deform by receiving the stress F2.
  • the pellicle film 12 is relieved of the tensile stress F1 received from the Si border 11, and cracking of the pellicle film 12 can be suppressed.
  • the thermal expansion coefficient of SiC is larger than that of Si. Therefore, when the temperature of the pellicle 1 changes, each of the Si border 11 and the pellicle film 12 expands or compresses, and the magnitude of the tensile stress F1 varies. The inventors of the present application have found that variations in the tensile stress F1 due to temperature changes in the pellicle 1 also cause cracks in the pellicle film 12 .
  • the Si border 11 receives compressive stress F2 and is easily deformed. As a result, variations in the magnitude of the tensile stress F1 due to temperature changes in the pellicle 1 are mitigated by the deformation of the Si layer 113, and cracking of the pellicle film 12 can be suppressed.
  • Si crystals of Si layer 113 which is an underlying layer, are different from SiC crystals in pellicle film 12.
  • a tensile stress F1 which is a force for alignment with the Si crystal, is applied. This is because the lattice constant of SiC is smaller than that of Si.
  • the Young's modulus of Si layer 113 is reduced, the tensile stress F1 applied by the Si crystals of Si layer 113 to the SiC crystals in pellicle film 12 is reduced. becomes smaller. As a result, cracking of the pellicle film 12 can be suppressed.
  • the inventors of the present application found that the Si substrate 113 cracked during the wet etching of the Si substrate 113 (while the Si substrate 113 was immersed in a chemical solution) during the manufacturing of the pellicle 1, and the pellicle film 12 peeled off from the Si substrate 113. I noticed something. The inventors of the present application believe that the reason for this is that the chemical solution after the reaction locally stays on the reaction surface of the Si substrate 113 (the surface of the portion of the back surface 113b of the Si substrate 113 that reacts with the chemical solution), thereby etching the Si. It was found that the speed became non-uniform and the reaction surface of the Si substrate 113 was roughened.
  • the inventors of the present application have found that when a mixed acid is used as a chemical solution for wet etching, large bubbles generated by the reaction between the chemical solution and Si locally stay on the reaction surface of the Si substrate 113, and the bubbles are generated by the Si substrate 113. It was found that the reaction surface of the Si substrate 113 was locally prevented from reacting with the chemical solution, and the reaction surface of the Si substrate 113 was roughened.
  • the mechanical strength of the pellicle film 12 itself is high, so the roughening of the reaction surface of the Si substrate 113 does not adversely affect the pellicle film 12 so much.
  • the pellicle film 12 is relatively thin (for example, when the thickness is 10 ⁇ m or less, specifically when it is a thin film (thickness of about several ⁇ m) or when it is an extremely thin film (thickness of the order of 100 nm or less), In this case, the roughening of the reaction surface of the Si substrate 113 adversely affects the pellicle film 12.
  • the roughening of the reaction surface of the Si substrate 113 applies non-uniform stress to the pellicle film 12, causing the pellicle film to undergo stress during Si etching. 12 may be cracked or the pellicle film 12 may be peeled off from the Si substrate 113 .
  • the Si substrate 113 and the pellicle film 12 are moved relative to the chemical solution for the wet etching, thereby localizing the reaction surface of the Si substrate 113. It is possible to prevent the chemicals and bubbles after the reaction from staying, and to prevent the reaction surface of the Si substrate 113 from being roughened. As a result, application of nonuniform stress to the pellicle film 12 can be suppressed, and the thickness of the pellicle film 12 can be reduced.
  • the pellicle film 12 is exposed to the chemical solution during wet etching.
  • the back surface 12b of the pellicle film 12 is exposed at the bottom of the recess 16.
  • the surface 12a of the pellicle film 12 is not exposed to the chemical solution during wet etching. Therefore, damage to the pellicle film 12 caused by the chemical can be minimized.
  • FIG. 16 is a cross-sectional view showing the configuration of the pellicle 1 according to the second embodiment of the invention. 16 is a cross-sectional view taken along a plane perpendicular to the surface 12a of the pellicle film 12. FIG.
  • the pellicle 1 of the present embodiment differs from the pellicle of the first embodiment in that it further includes an adhesive film 17 (an example of an adhesive film).
  • Adhesive film 17 is provided between the Si border 11 and the pellicle film 12 and bonds the Si border 11 and the pellicle film 12 together.
  • Adhesive film 17 is made of any material, such as acrylic resin adhesive, epoxy resin adhesive, polyimide resin adhesive, silicone resin adhesive, inorganic adhesive, double-sided adhesive tape, silicone resin adhesive, acrylic adhesive, and the like. It is made of adhesive or polyolefin adhesive.
  • FIG. 17 a method for manufacturing the pellicle 1 according to the present embodiment will be described with reference to FIGS. 17 to 21.
  • FIG. 17 a method for manufacturing the pellicle 1 according to the present embodiment will be described with reference to FIGS. 17 to 21.
  • a disk-shaped Si substrate (sacrificial substrate) 21 is prepared.
  • the (111) plane is exposed on the rear surface 21 a of the Si substrate 21 .
  • the (100) plane or the (110) plane may be exposed on the rear surface 21a of the Si substrate 21 .
  • the pellicle film 12 is formed on the rear surface 21a of the Si substrate 21.
  • the pellicle film 12 is formed, for example, on an underlying layer made of SiC obtained by carbonizing the back surface 21a of the Si substrate 21, using the MBE method, the CVD method, or the like.
  • the pellicle film 12 may be formed only by carbonizing the back surface 21 a of the Si substrate 21 .
  • the pellicle film 12 may be formed on the rear surface 21a of the Si substrate 21 using the MBE method, the CVD method, or the like.
  • any substrate can be used as the base of the pellicle film 12, but the substrate may be determined in consideration of the crystallinity of the pellicle film 12, which is the upper layer, ease of removal in a post-process, and the like. preferable.
  • a quartz substrate or the like may be used instead of the Si substrate 21 as the substrate that serves as the base of the pellicle film 12 .
  • a disk-shaped Si substrate 113 (without through-holes 13 formed therein) is prepared.
  • the Si substrate 113 contains B.
  • B is implanted into the Si substrate 113 by a method such as thermal diffusion or ion implantation.
  • Si border 11 made of the Si substrate 113 is produced by forming the through hole 13 in the Si substrate 113 .
  • Si border 11 has an annular planar shape surrounding through hole 13 .
  • a method for forming the through holes 13 is arbitrary, and a method such as mechanical grinding or etching may be used.
  • the back surface 12b of the pellicle film 12 and the Si border 11 are adhered using an adhesive.
  • the back surface 12b of the pellicle film 12 is the main surface opposite to the main surface (front surface 12a) of the pellicle film 12 on which the Si substrate 21 exists.
  • An adhesive film 17 is formed between the pellicle film 12 and the Si border 11 .
  • the intermediate 2 including the Si substrate 21, the pellicle film 12, the Si border 11, and the adhesive film 17 is obtained.
  • the Si substrate 21 is removed from the intermediate 2 with reference to FIG. As a result, the entire surface 12a of the pellicle film 12 is exposed.
  • the thickness of the Si substrate 21 is first reduced to an arbitrary thickness by removing Si by a method having a relatively high Si removal rate (for example, mechanical polishing), followed by It is preferable to completely remove the Si substrate 21 by removing Si by a method having a relatively slow Si removal rate (for example, wet etching).
  • a relatively high Si removal rate for example, mechanical polishing
  • a relatively slow Si removal rate for example, wet etching
  • Wet etching of Si is preferably performed by moving the intermediate 2 relative to the chemical solution.
  • Wet etching of Si is preferably performed by any one of the first to third methods (FIGS. 11 to 13) of wet etching of Si in the first embodiment.
  • the wet etching target is not the Si substrate 113 but the Si substrate 21 . Therefore, when using the first method (FIG. 11), the preform 2 is fixed to the fixing table HP so that the surface 21b of the Si substrate 21 faces upward. Then, the chemical solution MA is injected onto the surface 21b of the Si substrate 21 while the intermediate 2 is rotated without changing its position. Also when using the third method (FIG. 13), the preform 2 is fixed to the fixing table HP so that the surface 21b of the Si substrate 21 faces upward. Then, the intermediate body 2 and the fixed table HP are reciprocated in a straight line.
  • the configuration and manufacturing method of the pellicle 1 other than those described above are the same as the configuration and manufacturing method of the pellicle according to the first embodiment, so description thereof will not be repeated.
  • the Si substrate 21 is completely removed after the pellicle film 12 is formed, a process for etching a part of the Si substrate 21 (a process of patterning a photoresist or a hard mask, removal step, etc.) can be omitted.
  • the manufacturing process can be simplified, and the manufacturing cost of the pellicle can be reduced.
  • the pellicle film 12 is supported by the Si border 11, the pellicle film 12 can be made thinner while ensuring the mechanical strength of the pellicle film 12.
  • the wet etching of the Si substrate 21 may cause cracks in the pellicle film 12 during the wet etching of the Si substrate 21, or cracks may occur in the Si substrate 21. It is possible to prevent the pellicle film 12 from peeling off from the pellicle 1 and to reduce the thickness of the pellicle film 12 in the pellicle 1 .
  • the inventors of the present application confirmed the effect of improving the mechanical strength of the pellicle film by including the Si layer containing B in the border. Specifically, the following samples A to D were produced, and the yield rate of each of samples A to D was examined.
  • Sample A (example of the present invention): The pellicle shown in FIG. 1 was produced using the manufacturing method shown in the first embodiment.
  • the Si layer the one whose B concentration was adjusted so that the resistivity of the Si layer was in the range of 0 or more and 0.005 ⁇ cm or less was used.
  • Sample B (example of the present invention): As the Si layer, a layer was used in which the B concentration was adjusted so that the resistivity of the Si layer was greater than 0.005 ⁇ cm and less than or equal to 0.02 ⁇ cm. A pellicle 1 was manufactured in the same manufacturing method as the sample A except for this.
  • Sample C (example of the present invention): As the Si layer, a layer was used in which the B concentration was adjusted so that the resistivity of the Si layer was in the range of 1 ⁇ cm or more and 100 ⁇ cm or less. A pellicle 1 was manufactured in the same manufacturing method as the sample A except for this.
  • Sample D (comparative example): A Si layer not doped with B was used as the Si layer. Pellicle 1 was produced in the same manufacturing method as sample A except for this.
  • FIG. 22 is a diagram showing the yield rate of each of samples A to D in one example of the present invention.
  • the yield rate of sample A is 100%
  • the yield rate of sample B is 63%
  • the yield rate of sample C is 30%
  • the yield rate of sample D is 15%.
  • most of the cause of the decrease in the yield rate was the breakage of the pellicle film during the formation of through-holes in the Si layer by wet etching of the Si layer (during the process shown in FIG. 10).
  • the pellicle film may be made of materials other than SiC, such as Si, SiN, or C (graphite, graphene, diamond-like carbon (DLC), amorphous carbon, etc.).
  • SiC silicon, SiN, or C
  • DLC diamond-like carbon
  • the pellicle film made of SiC can improve the transparency of the pellicle film to the exposure light and the resistance to the exposure light while suppressing cracking of the pellicle film when the pellicle film is thinned.
  • the shape of the border is arbitrary.
  • planar shape of the pellicle 1 of the second embodiment may be as shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Vapour Deposition (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : une pellicule capable de supprimer la fissuration d'un film pelliculaire ; et un procédé de fabrication de la pellicule. La solution selon l'invention porte sur une pellicule qui comprend : une bordure de silicium (Si) comprenant une couche de Si contenant du bore (B) ; et un film pelliculaire formé sur un côté de surface de la couche de Si. De préférence, la bordure de Si comprend un trou traversant et le film pelliculaire est exposé sur la surface inférieure du trou traversant.
PCT/JP2022/005846 2021-02-17 2022-02-15 Pellicule et procédé de fabrication de pellicule WO2022176833A1 (fr)

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JP2021023790A JP2022125937A (ja) 2021-02-17 2021-02-17 ペリクルおよびペリクルの製造方法
JP2021-023790 2021-02-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298330A (ja) * 1998-10-28 2005-10-27 Asahi Glass Co Ltd 合成石英ガラスおよびその製造方法
JP2016200616A (ja) * 2015-04-07 2016-12-01 信越化学工業株式会社 ペリクル用フレーム及びそれを用いたペリクル
US20180284599A1 (en) * 2017-03-28 2018-10-04 Samsung Electronics Co., Ltd. Pellicle for exposure to extreme ultraviolet light, photomask assembly, and method of manufacturing the pellicle
JP2019032444A (ja) * 2017-08-08 2019-02-28 エア・ウォーター株式会社 ペリクルおよびペリクルの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298330A (ja) * 1998-10-28 2005-10-27 Asahi Glass Co Ltd 合成石英ガラスおよびその製造方法
JP2016200616A (ja) * 2015-04-07 2016-12-01 信越化学工業株式会社 ペリクル用フレーム及びそれを用いたペリクル
US20180284599A1 (en) * 2017-03-28 2018-10-04 Samsung Electronics Co., Ltd. Pellicle for exposure to extreme ultraviolet light, photomask assembly, and method of manufacturing the pellicle
JP2019032444A (ja) * 2017-08-08 2019-02-28 エア・ウォーター株式会社 ペリクルおよびペリクルの製造方法

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