WO2023074899A1 - ペリクルフレーム及びペリクル - Google Patents
ペリクルフレーム及びペリクル Download PDFInfo
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- WO2023074899A1 WO2023074899A1 PCT/JP2022/040734 JP2022040734W WO2023074899A1 WO 2023074899 A1 WO2023074899 A1 WO 2023074899A1 JP 2022040734 W JP2022040734 W JP 2022040734W WO 2023074899 A1 WO2023074899 A1 WO 2023074899A1
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- WIPO (PCT)
- Prior art keywords
- pellicle
- frame
- layer
- outermost
- pellicle frame
- Prior art date
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Images
Classifications
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- 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
-
- 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
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
- G03F1/84—Inspecting
-
- 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 pellicle frame and a pellicle that are mounted as dust guards for photomasks for lithography used in the manufacture of semiconductors, liquid crystals, etc., and particularly to a pellicle frame and pellicle for EUV.
- the above-mentioned semiconductors for example, semiconductors such as LSIs and VLSIs, are generally manufactured by applying a resist to a semiconductor wafer and then placing it in an exposure machine together with a photomask for lithography on which a desired circuit pattern is drawn. A photomask is irradiated with light to transfer a circuit pattern onto a semiconductor wafer. Normally, these operations are performed in a clean room where dust is reduced as much as possible, but even then, dust from the human body, equipment, or the environment often adheres to the mask when it is moved or installed after the mask is made. Since these dusts are transferred together with the circuit pattern, an abnormal circuit occurs, and the obtained semiconductor becomes a defective product, resulting in a decrease in manufacturing yield.
- Non-Patent Document 1 it is common practice to attach a dust-repellent pellicle to the mask immediately after making the mask. This is because if the pellicle is attached to the mask all at once, even if there is dust flying in, it is blocked by the pellicle and cannot reach the circuit pattern of the mask. Therefore, by focusing the exposure on the circuit pattern, the dust on the pellicle is not transferred as "out of focus".
- the pellicle is generally composed of a metal frame, a pellicle film having high transparency and light resistance to the exposure wavelength, and a pellicle film stretched on the upper end surface of the frame with an adhesive, and formed on the lower end surface of the frame. , an airtight seal using an adhesive such as acrylic or silicone, which is relatively light resistant, and a ventilation hole drilled in the frame to reduce the difference in air pressure between the inside and outside of the pellicle after it is attached to the mask. It has a blocking filter.
- the pellicle film is required to have high transmittance to the exposure wavelength and to have high light resistance.
- Amorphous fluorine polymer is used for KrF excimer laser (248 nm) and ArF excimer laser (193 nm).
- KrF excimer laser 248 nm
- ArF excimer laser (193 nm).
- materials with high transmittance and high light resistance to EUV light are selected, and usually inorganic materials are preferred over organic materials.
- monocrystalline silicon, polycrystalline silicon, amorphous silicon, or nitrides, oxynitrides, carbides thereof, metal silicides such as molybdenum silicide, or CNF, etc. which are inexpensive and capable of forming uniform films with good reproducibility.
- conventional pellicles that use transmitted light for exposure such as g-line (436 nm), i-line (365 nm), KrF excimer laser (248 nm), and ArF excimer laser used under atmospheric pressure, are generally light.
- a relatively low-hardness Al or Al alloy (duralumin) frame is used.
- black alumite treatment is applied to increase the hardness of the surface and to prevent stray light caused by reflection from the frame.
- alumite treatment is performed by anodic oxidation, and a black pigment or dye is put into the generated pores to perform a sealing treatment.
- the sealing treatment is not always perfect, and many voids and crater-like irregularities exist on the surface. Dust and foreign matter remaining during processing and anodizing, or part of the enclosed pigments and dyes, are often discharged from these unevenness and holes caused by the alumite treatment. It is a problem in terms of chemistry. Therefore, in general, in the case of rough devices for long-wave exposure, the anodized aluminum frame is often used as it is, but in the case of fine devices for short-wave exposure, these voids and craters are processed. A material intended to prevent the discharge of residual dust, foreign matter, or pigments and dyes during black alumite treatment is used (see Non-Patent Document 1 for details).
- the pellicle membrane is stretched on the frame, and the air vent filter is made of, for example, non-woven fabric such as PET or PTFE, which has a fiber diameter of several tens of microns to several hundreds of microns. .
- a pellicle for EUV extreme ultraviolet rays; 13.5 nm
- EUV extreme ultraviolet rays
- a conventional Al or Al alloy denseumin
- it is relatively light, has higher strength and hardness than Al and Al alloys, is difficult to deform, has corrosion resistance, and does not require black alumite treatment, which is a problem in terms of cleaning, Ti or Ti alloys.
- Patent Document 1 discloses a pellicle frame made of Ti or a Ti alloy having a coefficient of linear expansion of 10 ⁇ 10 ⁇ 6 (1/K) or less and a density of 4.6 g/cm 3 or less. It discloses a pellicle frame made of Ti having a thickness of less than 2.5 mm and having at least one notch extending from the outer surface to the inner surface of the end face.
- EUV exposure uses reflected light, so it is affected by the need to secure space for the long reflected light path. It has limited space. Due to such space restrictions and their intended use, pellicle frames are also required to have more precise processing accuracy than before, as well as thorough prevention and cleanliness control of submicron dust and foreign matter.
- Ti or Ti alloy which has a higher surface hardness than Al or Al alloy and is easy to improve processing accuracy, is used.
- chemical polishing such as electropolishing is performed, and the frame surface, openings, etc. It enhances the smoothness of
- the present invention has been made in view of such circumstances. To provide a pellicle frame and a pellicle using the same, which can suppress the generation of dust and foreign matter generated in the and
- a frame base material made of Ti or a Ti alloy
- a pellicle frame having a metal layer laminated on the surface of the frame base material, the metal layer comprises one or more layers
- the surface of the pellicle frame has an outermost surface layer of the metal layer
- a pellicle frame having an area with an arithmetic mean surface roughness Ra of 0.10 ⁇ m or less on at least the inner surface when the surface of the outermost surface layer is measured at a magnification of 1200 using a laser microscope in accordance with JIS B0601.
- a method for manufacturing a pellicle comprising the following steps (1) to (3), which are performed in the stated order.
- step (3) when the surface of the outermost surface layer is measured at a magnification of 1200 using a laser microscope in accordance with JIS B0601, at least the inner surface has an arithmetic mean surface roughness Ra of 0. .
- New pellicle frames, pellicles, and exposure master plates with pellicles can be used to suppress the generation of new dust and foreign matter during use, and even if dust or foreign matter adheres to the frame, they can be easily washed off. can provide.
- FIG. 1 is a perspective view showing an example of a pellicle frame of the present invention
- the present inventors mutually complemented these mutually insufficient parts, specified a magnification of 1200 times as a method that enables grasping of the overall image and observation of details, and non-contact " It was found that observation and calculation of the arithmetic mean surface roughness Ra according to JIS B0601 using a "laser microscope” is suitable for quantitatively grasping the relative smoothness of the entire frame. As can be seen in FIG. 1, when observing the surface roughness Ra at magnifications of 1,200, 3,600, and 7,200 using a "laser microscope", it is too fine to grasp the whole image at 3,600 and 7,200. On the other hand, observation at 1200 times is preferable for showing the details of the outermost surface and overall information required for the frame of the EUV pellicle of the present invention in a well-balanced manner. is.
- the inventors of the present invention found that the ridges and valleys of the frame are like a “garbage reservoir” and “garbage generator” for dust and foreign matter, and diligently studied measures to improve it.
- the frame base material is subjected to physical and/or chemical treatment in advance, smoothed and cleaned, and at least one layer of metal is laminated on this surface layer, the above-mentioned "garbage collection” can be achieved. It was found that the remaining dust and foreign matter can be fixed as if the ⁇ garbage generator'' was covered, and that it functions as a reinforcing layer for irregular portions that generate new dust and foreign matter, thereby suppressing them.
- the surface layer smoothed by subjecting the frame base material to the above-mentioned physical and/or chemical treatment is at least on the inner surface, at least with a laser microscope (under observation at a magnification of 1200). , an area having an arithmetic mean surface roughness Ra of 0.30 ⁇ m or less according to JIS B0601. This is because when the arithmetic mean surface roughness Ra is 0.30 ⁇ m or less, if at least one layer of metal is laminated on the surface layer, even if the thickness of the laminated film is somewhat thin, dust, foreign matter, or the like remaining in the ridges and valleys can be eliminated.
- the irregular parts are fixed or sufficiently reinforced, so that it becomes a so-called "garbage bin or dust generator lid", and it is possible to suppress the discharge of remaining dust and foreign matter and the generation of new dust and foreign matter.
- the surface has a rough surface with an arithmetic mean surface roughness Ra of more than 0.30 ⁇ m, the peaks and valleys are too high or too deep, and even the metal lamination can completely create a “dust pool” or “dust generator.” This is because the fixation and reinforcement of "" will be insufficient, and the effect of the invention will be reduced.
- the arithmetic mean surface roughness Ra of the surface of the frame base material may be calculated by measuring the surface of the frame base material with a laser microscope or the like according to JIS B0601:1994. Specifically, in observing the surface of the frame base material, in accordance with JIS B0601: 1994, using a laser microscope VK-3000 manufactured by Keyence Corporation, under the condition of a magnification of 1200 times (objective lens magnification of 50 times). Ra was measured at 30 random points in the screen, and the average value of the Ra at 30 points was taken as the value of the arithmetic mean surface roughness Ra.
- the arithmetic mean surface roughness Ra is obtained by extracting only the reference length from the roughness curve in the direction of the average line, taking the X axis in the direction of the average line of this sampled portion, and the Y axis in the direction of the longitudinal magnification.
- the value obtained by the following formula is expressed in micrometers ( ⁇ m).
- 30-point measurement 30 lines with a cutoff length of 250 ⁇ m are selected at intervals of 3 ⁇ m at the center of each side inner side surface of the frame base material, which is the object, and measurements are performed. is obtained from the above formula, and the average value thereof is calculated as the arithmetic average surface roughness Ra of 30 points.
- the method of measuring the arithmetic mean surface roughness Ra of the inner side surface of the frame base material has been described as an example, but the arithmetic mean surface roughness Ra of the inner side surface of the pellicle frame is also measured by the same method. is possible.
- the metal layered on the frame member that is, the metal forming the metal layer may be any metal that has an affinity with Ti or a Ti alloy. If it is to be used as the outermost surface layer, since the outermost surface layer is easily peeled off, a metal having an affinity for both Ti or a Ti alloy and the metal constituting the outermost surface layer is laminated on the frame member as an underlayer. A metal having no affinity for Ti or a Ti alloy may be laminated on the metal, which costs more but does not cause peeling of the outermost surface layer. Therefore, the metal layer may be composed of a single layer or multiple layers. Also, the type of metal to be laminated is not particularly limited, but metals having an extreme difference in coefficient of thermal expansion from Ti or Ti alloy of the frame base material should be avoided.
- the metal that finally constitutes the outermost surface layer of the frame may be Ti or Ti alloy when transporting, mounting, or using the frame and the pellicle using it.
- the thickness of the outermost surface layer of the metal layer is preferably determined in consideration of its coefficient of thermal expansion. Insufficient reinforcement and reinforcement, and do not exhibit sufficient effects. On the other hand, if the thickness is more than 50 ⁇ m, the frame is likely to deform due to thermal stress between the base material of the frame and the laminated metal due to the difference in thermal expansion coefficient. or deformation of the exposure pattern is likely to occur. Therefore, the thickness of the outermost surface layer is usually preferably in the range of 0.10 to 50 ⁇ m, but is ultimately determined by performance/cost.
- Methods for laminating this metal on the frame base material include physical methods such as the sputtering method, EB method, and MBE method, and chemical methods such as the MOCVD method, the LTCVD method, and electrolysis and electroless plating. Although it is not particularly limited, the LTCVD method and various electrolytic and electroless plating methods are suitable from the viewpoint of film thickness uniformity.
- the remaining dust and foreign matter are fixed, and irregular parts are reinforced to prevent dust and foreign matter from being discharged and generated. be done. Also, even if dust or foreign matter adheres to the frame, it can be easily washed off.
- the detection and management of pellicles and pellicle frames, especially dust and foreign matter on EUV pellicles and their frames, should normally be detected and managed at the EUV wavelength used.
- a measuring instrument since such a measuring instrument is extremely expensive, at present, the measurement is often carried out with a measuring instrument having a wavelength of at least 550 nm or less for convenience. Therefore, in the pellicle frame of the present invention, the surface reflectance of the outermost layer of the metal layer is preferably 20.0% or more when measured at least at a wavelength of 550 nm.
- the reflectance is less than 20.0% in the detection and management of microscopic dust and foreign matter, which are problematic for EUV. This is because if it is 0% or more, the contrast of dust and foreign matter is likely to appear, the sensitivity is increased, and accurate measurement can be performed. From the viewpoint of the reflectance, it is necessary that the arithmetic mean surface roughness Ra of the outermost surface layer of the laminated metal layer is 0.10 ⁇ m or less by a laser microscope (under observation at 1200 times) in order to increase the reflectance. is also suitable.
- the reflectance can be measured by irradiating the outermost surface layer of the pellicle frame with light.
- the outermost surface layer is irradiated with light having a wavelength of 550 nm, and the average value of the measured values can be used as the reflectance of the surface of the outermost surface layer.
- the pellicle manufacturing method of the present invention is characterized by including the following steps (1) to (3), which are performed in the order described.
- FIG. 2 shows an example of the pellicle frame of the present invention.
- Reference numeral 11 denotes the inner surface of the pellicle frame
- 12 denotes the outer surface of the pellicle frame
- 13 denotes the upper end surface of the pellicle frame
- 14 denotes the lower end surface of the pellicle frame. indicates the central portion of the inner surface of the pellicle frame.
- jig holes used for peeling the pellicle from the photomask are provided on the long side of the pellicle frame, but they are not shown in FIG.
- a pellicle film is provided on the upper end surface of the pellicle frame via an adhesive.
- an adhesive such as an acrylic resin, a silicone resin, or an epoxy resin may be used.
- the material of the pellicle film is not limited, it preferably has high transmittance at the wavelength of the exposure light source and high light resistance.
- an amorphous fluoropolymer or the like can be used for an excimer laser.
- amorphous fluoropolymers include CYTOP [manufactured by Asahi Glass Co., Ltd.: trade name], Teflon (registered trademark) AF [manufactured by DuPont Co., Ltd.: trade name], and the like.
- a protective film such as SiC, SiO2 , Si3N4 , SiON, Y2O3 , YN, Mo, Ru and Rh may be provided.
- an adhesive layer for attachment to a photomask is formed on the lower end surface of the pellicle frame.
- the mask adhesive known ones can be used, and adhesives made of polybutene resin, polyvinyl acetate resin, SEBS (poly(styrene-ethylene-butadiene-styrene)) resin, acrylic resin, silicone resin, etc. can be used. can be used. Adhesives made of acrylic resins and silicone resins are particularly preferred.
- the pellicle film adhesive and mask adhesive can be applied, for example, by dipping, spraying, brushing, or using a dispenser-based coating device. , yield and the like.
- aromatic solvents such as toluene and xylene, hexane, octane, isooctane, isoparaffin, etc.
- aromatic solvents such as toluene and xylene, hexane, octane, isooctane, isoparaffin, etc.
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
- ester solvents such as ethyl acetate and butyl acetate
- ether solvents such as diisopropyl ether and 1,4-dioxane, or mixed solvents thereof.
- a release layer may be attached to the lower end surface of the mask adhesive to protect the adhesive.
- the material of the release layer is not particularly limited, but for example polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyethylene (PE), polycarbonate (PC ), polyvinyl chloride (PVC), polypropylene (PP), etc. can be used.
- a release agent such as a silicone-based release agent or a fluorine-based release agent may be applied to the surface of the release layer.
- a dust removal filter may be provided for the purpose of removing particles.
- the filter may be placed inside the hole, or it may be placed on the side to cover the opening of the hole.
- the adhesive layer is usually applied and formed first, and then the pellicle film is stretched, but the order may be reversed.
- the pellicle film is stretched, for example, by applying an adhesive to the upper end surface of the pellicle frame, then heating the pellicle frame to harden the adhesive, and finally attaching the pellicle film to an aluminum frame larger than the pellicle frame.
- the upper end surface of the pellicle frame on which the adhesive layer for pellicle film attachment is formed is attached, and excess pellicle membrane protruding outside the pellicle frame is removed to complete the pellicle.
- a pellicle-attached exposure original plate is obtained by attaching the above pellicle to an exposure original plate such as a photomask via an adhesive layer.
- a pellicle is installed so as to surround the pattern area formed on the surface of the exposure original plate.
- a region having an arithmetic mean surface roughness Ra equal to or less than the above value may be provided in a portion of the frame base material or the inner surface of the pellicle frame.
- the entire inner surface more preferably the frame base material or the entire frame surface (i.e., the entire upper end surface, lower end surface, inner surface and outer surface of the frame base material or frame).
- a surface treatment can be applied to the frame base material or the pellicle frame so that it is less than or equal to the value. In this case, the frame base material or the pellicle frame may not be partially surface-treated.
- Example 1 After creating a pellicle frame (outer dimensions: 150 mm x 118 mm x 1.5 mm, frame thickness: 4.0 mm) using JIS Class 2 Ti, the surface and holes are polished using a polishing sheet and polishing slurry, and then washed. and finished to a mirror surface with the naked eye. After that, the pellicle frame is further polished by electropolishing, which is a chemical treatment, with a non-contact laser microscope (under observation of 1200 times) until the arithmetic mean surface roughness Ra in accordance with JIS B0601 reaches 0.12 ⁇ m. washed. A Ni metal layer having a thickness of 0.15 ⁇ m was deposited thereon by LPCVD and washed.
- the arithmetic mean surface roughness Ra according to JIS B0601 was 0.09 ⁇ m.
- the reflectance at a wavelength of 550 nm was 24%, and the Vickers hardness was 550 HV.
- a 0.1 ⁇ m polycrystalline Si film is stretched on this frame, and the air pressure adjustment vent of the frame is made of polypropylene fiber with an average diameter of 3 ⁇ m and electrospun silica fiber with an average diameter of 0.15 ⁇ m. was attached to prepare a pellicle for EUV.
- This pellicle was attached via an adhesive to a well-cleaned quartz glass plate simulating an exposure mask. After that, this quartz glass plate was mounted in a simulated EUV apparatus, and a simulation experiment was conducted in which air pressure was adjusted by alternately repeating evacuation and atmospheric pressure return assuming removal and removal of the mask, and the effect of the present invention was easily demonstrated. evaluated.
- the pellicle was removed from the virtual mask after the quartz glass plate, which was a virtual mask, was assumed to be moved in and out of the EUV apparatus 100 times by repeatedly vacuuming and returning to the atmospheric pressure. Dust and foreign matter were inspected with a laser foreign matter inspection device. As a result, as shown in Table 1, there was no dust or foreign matter with a diameter of 0.2 ⁇ m or more, and there was no dust or foreign matter with a diameter of less than 0.2 ⁇ m.
- Example 2 As in Example 1, a pellicle frame (outer dimensions: 150 mm x 118 mm x 1.5 mm, frame thickness: 4.0 mm) was prepared using JIS class 2 Ti. After polishing, wash it, finish it until it becomes a mirror surface with the naked eye, then electropolish a further chemical treatment, with a non-contact laser microscope (under observation at 1200 times), JIS B0601 compliant arithmetic average surface roughness The pellicle frame was polished and cleaned until Ra became 0.28 ⁇ m. It was assumed to be the same, including preparation and subsequent evaluation.
- the outermost surface layer after lamination and washing was measured with the above-mentioned non-contact laser microscope (under observation at 1200 times), and the arithmetic mean surface roughness Ra was 0.07 ⁇ m, and the reflectance at a wavelength of 550 nm was 75%. , Vickers hardness was 850HV. As shown in Table 1, the inspection results for dust and foreign matter on the quartz glass plate were zero for dust and foreign matter of 0.2 ⁇ m or more and one for dust and foreign matter of less than 0.2 ⁇ m.
- Example 1 As in Example 1, a pellicle frame (outer dimensions: 150 mm x 118 mm x 1.5 mm, frame thickness: 4.0 mm) was prepared using JIS class 2 Ti. After polishing, wash it, finish it until it becomes a mirror surface with the naked eye, then electropolish a further chemical treatment, with a non-contact laser microscope (under observation at 1200 times), JIS B0601 compliant arithmetic average surface roughness The pellicle frame was polished and cleaned until Ra became 0.23 ⁇ m. bottom. As shown in Table 1, the inspection results for dust and foreign matter on the quartz glass plate were 6 dust and foreign matter of 0.2 ⁇ m or more and 15 dust and foreign matter of less than 0.2 ⁇ m.
- a pellicle frame (outer dimensions: 150 mm x 118 mm x 1.5 mm, frame thickness: 4.0 mm) was prepared using JIS class 2 Ti. After polishing, wash it, finish it until it becomes a mirror surface with the naked eye, then electropolish a further chemical treatment, with a non-contact laser microscope (under observation at 1200 times), JIS B0601 compliant arithmetic average surface roughness The pellicle frame was polished and cleaned until Ra was 0.39 ⁇ m, except that instead of depositing Ni metal to a thickness of 0.15 ⁇ m by LPCVD, Ni metal was deposited by LPCVD to a thickness of 0.23 ⁇ m.
- Example 3 As in Example 1, a pellicle frame (outer dimensions: 150 mm x 118 mm x 1.5 mm, frame thickness: 4.0 mm) was prepared using JIS class 2 Ti. After polishing, wash it, finish it until it becomes a mirror surface with the naked eye, then electropolish a further chemical treatment, with a non-contact laser microscope (under observation at 1200 times), JIS B0601 compliant arithmetic average surface roughness The pellicle frame was polished and cleaned until Ra became 0.35 ⁇ m. It was assumed to be the same, including preparation and subsequent evaluation.
- the outermost surface layer after lamination and washing was measured with the non-contact laser microscope (observed at 1,200 times), and the arithmetic mean surface roughness Ra was 0.13 ⁇ m (partial crack generation), and the wavelength was 550 nm.
- the reflectance of the frame was deformed and could not be measured, and the Vickers hardness was 630 HV.
- Table 1 the inspection results of dust and foreign matter on the quartz glass plate were 53 pieces of dust and foreign matter of 0.2 ⁇ m or more and 135 pieces of dust and foreign matter of less than 0.2 ⁇ m.
- Pellicle frame 11 Pellicle frame inner surface 12 Pellicle frame outer surface 13 Pellicle frame upper end surface 14 Pellicle frame lower end surface P Center of inner surface
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Abstract
Description
[1] Ti又はTi合金からなるフレーム母材と、
前記フレーム母材の表面に積層された金属層とを有するペリクルフレームであって、
前記金属層が1又は複数の層を含み、
前記ペリクルフレームの表面が、前記金属層の最表面層を有し、
前記最表面層の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが、0.10μm以下の領域を有するペリクルフレーム。
[2] 前記最表面層の厚みが、0.10μm以上である前記[1]に記載のペリクルフレーム。
[3] 前記最表面層の厚みが、0.10μm以上50μm以下である前記[2]に記載のペリクルフレーム。
[4] 前記最表面層が、ビッカース硬度で160以上である前記[1]~[3]のいずれかに記載のペリクルフレーム。
[5] 前記最表面層を構成する主成分が、Ni及びCrのうち少なくとも1種である前記[1]~[4]のいずれかに記載のペリクルフレーム。
[6] 前記最表面層を構成する主成分が、Niである前記[5]に記載のペリクルフレーム。
[7] 前記最表面層を構成する主成分が、Crである前記[5]に記載のペリクルフレーム。
[8] 前記最表面層の表面の反射率が、波長550nmで測定したとき、20.0%以上である前記[1]~[7]のいずれかに記載のペリクルフレーム。
[9] 前記最表面層の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが、0.10μm以下の領域を有する前記[1]~[8]のいずれかに記載のペリクルフレーム。
[10] 前記[1]~[9] のいずれかに記載のペリクルフレームを有するペリクル。
[11] 前記ペリクルが、EUV用ペリクルである前記[10]に記載のペリクル。
[12] 露光原版に前記[10]又は[11]に記載のペリクルが装着されているペリクル付露光原版。
[13] 以下の(1)~(3)の工程を含み、この記載順に行うことを特徴とするペリクルの製造方法。
(1)Ti又はTi合金からなるフレーム母材を成形する工程、
(2)前記フレーム母材の表面に物理的研磨加工及び化学的研磨加工のいずれか一方又は両方を施し、該表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが0.30μm以下の領域を設ける工程、
(3)前記フレーム母材の表面に1又は複数の層を含む金属層よりなる最表面層を積層する工程。
[14] 前記工程(2)において、物理的研磨加工のみを行う前記[13]に記載の製造方法。
[15] 前記工程(2)において、化学的研磨加工のみを行う前記[13]に記載の製造方法。
[16] 前記工程(2)において、物理的研磨加工及び化学的研磨加工の両方をこの記載順に行う前記[13]に記載の製造方法。
[17] 前記工程(3)において、前記最表面層の厚みは0.10μm以上である前記[13]~[16]のいずれかに記載の製造方法。
[18] 前記工程(3)において、前記最表面層の厚みは0.10μm以上50μm以下である前記[17]に記載の製造方法。
[19] 前記工程(3)において、前記最表面層のビッカース硬度が160以上である前記[13]~[18]のいずれかに記載の製造方法。
[20] 前記工程(3)における前記最表面層の主成分が、Ni及びCrのうち少なくとも1種である前記[13]~[19]のいずれかに記載の製造方法。
[21] 前記最表面層の主成分が、Niである前記[20]に記載の製造方法。
[22] 前記最表面層の主成分が、Crである前記[20]に記載の製造方法。
[23] 前記工程(3)において、前記最表面層の表面の反射率が、波長550nmで測定したとき、20.0%以上である前記[13]~[22]のいずれかに記載の製造方法。
[24] 前記工程(3)において、前記最表面層の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが、0.10μm以下の領域を有する前記[13]~[23]のいずれかに記載の製造方法。
本発明者らは、ゴミ、異物の発塵源の根本原因の究明に努めた結果、Ti又はTi合金でペリクルのフレーム枠を形成した後、そのフレーム枠表面や開口部を砥石や砥粒、バフなどの物理的研磨及び/又は電解研磨などの化学的研磨し、洗浄された物でも肉眼上では、たとえ表面にゴミ、異物が無く、極めて平滑な、鏡面に見えたといえども、非接触のレーザー顕微鏡(例えば、キーエンス社製;VK-X3000;1200倍の視野)で観察してみると、図1の如く、実は無数の凹凸と言うより、大きな山谷が存在していることが分かった。この山谷の深みの部分に加工時のゴミ、異物が残存すると共に、更に山谷で衝撃に弱い、不整な箇所などから新たにゴミ、異物が生じることを見出した。これは、あたかも山谷部分が「ゴミ溜め」、「ゴミ発生器」の如き存在になっており、加工時はおろか、移動時、保管時、使用時などで、ゴミ、異物が際限無く執拗に検出される原因であり、皆無にするのが難しかった理由でもあることを把握した。
上記の30箇所測定については、対象物である前記フレーム母材の各辺内側面の中央部において、250μmのカットオフ長のラインを3μm間隔で30本を選定して測定を行い、各ラインそれぞれの算術平均表面粗さRaを上記式より求めて、それらの平均値を30箇所の算術平均表面粗さRaとして算出する。
なお、ここではフレーム母材を例にしてその内側面表面の算術平均表面粗さRaの測定方法について説明したが、ペリクルフレームの内側面表面の算術平均表面粗さRaについても同様な方法で測定が可能である。
(1)Ti又はTi合金からなるフレーム母材を成形する工程、
(2)前記フレーム母材の表面に物理的研磨加工及び化学的研磨加工のいずれか一方又は両方を施し、該表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが0.30μm以下の領域を設ける工程、
(3)前記フレーム母材の表面に1又は複数の層の金属層よりなる最表面層を積層する工程。
前記(3)の工程によりペリクルフレームの作成後は、該ペリクルフレームの一端面にペリクル膜を張設し、他端面に粘着剤層を設けるなど、通常の方法にしたがってペリクルが製造される。
図2に本発明のペリクルフレームの一例を示し、符号11はペリクルフレームの内側面、符号12はペリクルフレームの外側面、符号13はペリクルフレームの上端面、符号14はペリクルフレームの下端面、Pはペリクルフレームの内側面の中央部を示す。なお、通常、ペリクルフレームの長辺側にはペリクルをフォトマスクから剥離するために用いられる治具穴が設けられるが、図2では特に図示していない。
JIS2種のTiを用いてペリクルフレーム(外寸150mm×118mm×1.5mm、フレーム厚4.0mm)を作成後、研磨シート及び研磨スラリーの物理的処理で表面及び孔の部分を研磨後、洗浄し、肉眼で鏡面になるまで仕上げた。その後、更に化学的処理の電解研磨で、非接触のレーザー顕微鏡(1200倍の観察下)で、JIS B0601に準拠した算術平均表面粗さRaが0.12μmになるまで、前記ペリクルフレームを研磨・洗浄した。これにLPCVDでNi金属を0.15μm厚だけ積層し、洗浄した。その結果、この積層・洗浄後の最表面層は先の非接触のレーザー顕微鏡(1200倍の観察下)で測定したところ、JIS B0601に準拠した算術平均表面粗さRaが0.09μmであり、また波長550nmの反射率が24%、ビッカース硬度が550HVであった。このフレームに0.1μmの多結晶Si膜を張設し、更にフレームの気圧調整用通気口を平均径3μmのポリプロピレン・ファイバーとエレクトロスピンニングで作成した平均径0.15μmのシリカファイバーよりなるフィルターを貼り、EUV用ペリクルを作成した。このペリクルを、露光マスクに模した良く洗浄した石英ガラス板に接着剤を介して貼り付けた。その後、この石英ガラス板を模擬EUV装置に装着して、マスクの出し入れを想定した真空引きと大気圧戻しを交互に繰り返し、気圧調整を行ったシュミレーション実験を実施し、本発明の効果を簡便に評価した。なお、シュミレーション実験は、真空引きと大気圧戻しの繰り返しにより、仮想マスクたる石英ガラス板をEUV装置から100回の想定的出し入れを繰り返した後に、ペリクルを仮想マスクから外し、該石英ガラス板上のゴミ、異物をレーザー異物検査装置で検査した。その結果、表1に示したように、0.2μm以上のゴミ、異物はゼロ、0.2μm未満のゴミ、異物もゼロであった。
実施例1と同じくJIS2種のTiを用いてペリクルフレーム(外寸150mm×118mm×1.5mm、フレーム厚4.0mm)を作成後、研磨シート及び研磨スラリーの物理的処理で表面及び孔の部分を研磨後、洗浄し、肉眼で鏡面になるまで仕上げ、その後、更に化学的処理の電解研磨で、非接触のレーザー顕微鏡(1200倍の観察下)で、JIS B0601に準拠した算術平均表面粗さRaが0.28μmになるまで、前記ペリクルフレームを研磨・洗浄したが、その後のLPCVDでNi金属を0.15μm厚に積層する代わりに、メッキでCr金属を20μm厚に積層した以外は、ペリクル作成、その後の評価も含め同一とした。積層・洗浄後の最表面層は先の非接触のレーザー顕微鏡(1200倍の観察下)で測定したところ、算術平均表面粗さRaは0.07μmであり、また波長550nmの反射率は75%、ビッカース硬度は850HVであった。石英ガラス板上のゴミ、異物の検査結果は、表1に示したように、0.2μm以上のゴミ、異物はゼロ、0.2μm未満のゴミ、異物は1個であった。
実施例1と同じくJIS2種のTiを用いてペリクルフレーム(外寸150mm×118mm×1.5mm、フレーム厚4.0mm)を作成後、研磨シート及び研磨スラリーの物理的処理で表面及び孔の部分を研磨後、洗浄し、肉眼で鏡面になるまで仕上げ、その後、更に化学的処理の電解研磨で、非接触のレーザー顕微鏡(1200倍の観察下)で、JIS B0601に準拠した算術平均表面粗さRaが0.23μmになるまで、前記ペリクルフレームを研磨・洗浄したが、その後のLPCVDでNi金属を0.15μm厚に積層することを省いた以外は、ペリクル作成、その後の評価も含め同一とした。石英ガラス板上のゴミ、異物の検査結果は、表1に示したように、0.2μm以上のゴミ、異物は6個で、0.2μm未満のゴミ、異物は15個であった。
実施例1と同じくJIS2種のTiを用いてペリクルフレーム(外寸150mm×118mm×1.5mm、フレーム厚4.0mm)を作成後、研磨シート及び研磨スラリーの物理的処理で表面及び孔の部分を研磨後、洗浄し、肉眼で鏡面になるまで仕上げ、その後、更に化学的処理の電解研磨で、非接触のレーザー顕微鏡(1200倍の観察下)で、JIS B0601に準拠した算術平均表面粗さRaが0.39μmになるまで、前記ペリクルフレームを研磨・洗浄したが、その後のLPCVDでNi金属を0.15μm厚に積層する代わりに、LPCVDでNi金属を0.23μm厚に積層した以外は、ペリクル作成、その後の評価も含め同一とした。積層・洗浄後の最表面層は先の非接触のレーザー顕微鏡(1200倍の観察下)で測定したところ、算術平均表面粗さRaは0.19μmであり、また波長550nmの反射率は26%、ビッカース硬度は557HVであった。石英ガラス板上のゴミ、異物の検査結果は、表1に示したように、0.2μm以上のゴミ、異物は4個、0.2μm未満のゴミ、異物は13個であった。
実施例1と同じくJIS2種のTiを用いてペリクルフレーム(外寸150mm×118mm×1.5mm、フレーム厚4.0mm)を作成後、研磨シート及び研磨スラリーの物理的処理で表面及び孔の部分を研磨後、洗浄し、肉眼で鏡面になるまで仕上げ、その後、更に化学的処理の電解研磨で、非接触のレーザー顕微鏡(1200倍の観察下)で、JIS B0601に準拠した算術平均表面粗さRaが0.35μmになるまで、前記ペリクルフレームを研磨・洗浄したが、 その後のLPCVDでNi金属を0.15μm厚に積層する代わりに、メッキでNi金属を55μm厚に積層した以外は、ペリクル作成、その後の評価も含め同一とした。積層・洗浄後の最表面層は先の非接触のレーザー顕微鏡(1200倍の観察下)で測定したところ、算術平均表面粗さRaが0.13μm(一部クラック発生)であり、また波長550nmの反射率はフレームが変形して測定不可、ビッカース硬度は630HVであった。石英ガラス板上のゴミ、異物の検査結果は、表1に示したように、0.2μm以上のゴミ、異物は53個、0.2μm未満のゴミ、異物は135個であった。
11 ペリクルフレームの内側面
12 ペリクルフレームの外側面
13 ペリクルフレームの上端面
14 ペリクルフレームの下端面
P 内側面の中央部
Claims (24)
- Ti又はTi合金からなるフレーム母材と、
前記フレーム母材の表面に積層された金属層とを有するペリクルフレームであって、
前記金属層が1又は複数の層を含み、
前記ペリクルフレームの表面が、前記金属層の最表面層を有し、
前記最表面層の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが、0.10μm以下の領域を有するペリクルフレーム。 - 前記最表面層の厚みが、0.10μm以上である請求項1に記載のペリクルフレーム。
- 前記最表面層の厚みが、0.10μm以上50μm以下である請求項2に記載のペリクルフレーム。
- 前記最表面層が、ビッカース硬度で160以上である請求項1~3のいずれか1項に記載のペリクルフレーム。
- 前記最表面層を構成する主成分が、Ni及びCrのうち少なくとも1種である請求項1~4のいずれか1項に記載のペリクルフレーム。
- 前記最表面層を構成する主成分が、Niである請求項5に記載のペリクルフレーム。
- 前記最表面層を構成する主成分が、Crである請求項5に記載のペリクルフレーム。
- 前記最表面層の表面の反射率が、波長550nmで測定したとき、20.0%以上である請求項1~7のいずれか1項に記載のペリクルフレーム。
- 前記フレーム母材の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが0.30μm以下の領域を有する請求項1~8のいずれか1項に記載のペリクルフレーム。
- 請求項1~9のいずれか1項に記載のペリクルフレームを有するペリクル。
- 前記ペリクルが、EUV用ペリクルである請求項10に記載のペリクル。
- 露光原版に請求項10又は11に記載のペリクルが装着されているペリクル付露光原版。
- 以下の(1)~(3)の工程を含み、この記載順に行うことを特徴とするペリクルの製造方法。
(1)Ti又はTi合金からなるフレーム母材を成形する工程、
(2)前記フレーム母材の表面に物理的研磨加工及び化学的研磨加工のいずれか一方又は両方を施し、該表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが0.30μm以下の領域を設ける工程、
(3)前記フレーム母材の表面に1又は複数の層を含む金属層よりなる最表面層を積層する工程。 - 前記工程(2)において、物理的研磨加工のみを行う請求項13に記載の製造方法。
- 前記工程(2)において、化学的研磨加工のみを行う請求項13に記載の製造方法。
- 前記工程(2)において、物理的研磨加工及び化学的研磨加工の両方をこの記載順に行う請求項13に記載の製造方法。
- 前記工程(3)において、前記最表面層の厚みは0.10μm以上である請求項13~16のいずれか1項に記載の製造方法。
- 前記工程(3)において、前記最表面層の厚みは0.10μm以上50μm以下である請求項17に記載の製造方法。
- 前記工程(3)において、前記最表面層のビッカース硬度が160以上である請求項13~18のいずれか1項に記載の製造方法。
- 前記工程(3)における前記最表面層の主成分が、Ni及びCrのうち少なくとも1種である請求項13~19のいずれか1項に記載の製造方法。
- 前記最表面層の主成分が、Niである請求項20に記載の製造方法。
- 前記最表面層の主成分が、Crである請求項20に記載の製造方法。
- 前記工程(3)において、前記最表面層の表面の反射率が、波長550nmで測定したとき、20.0%以上である請求項13~22のいずれか1項に記載の製造方法。
- 前記工程(3)において、前記最表面層の表面をJIS B0601に準拠してレーザー顕微鏡を用いて1200倍の倍率で測定したとき、少なくとも内側面に算術平均表面粗さRaが、0.10μm以下の領域を有する請求項13~23のいずれか1項に記載の製造方法。
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