WO2014103867A1 - 位相シフトマスクおよびその製造方法 - Google Patents

位相シフトマスクおよびその製造方法 Download PDF

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Publication number
WO2014103867A1
WO2014103867A1 PCT/JP2013/084059 JP2013084059W WO2014103867A1 WO 2014103867 A1 WO2014103867 A1 WO 2014103867A1 JP 2013084059 W JP2013084059 W JP 2013084059W WO 2014103867 A1 WO2014103867 A1 WO 2014103867A1
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Prior art keywords
phase shift
line
layer
transmittance
light
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PCT/JP2013/084059
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English (en)
French (fr)
Japanese (ja)
Inventor
聖 望月
中村　大介
影山　景弘
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アルバック成膜株式会社
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Application filed by アルバック成膜株式会社 filed Critical アルバック成膜株式会社
Priority to KR1020157015967A priority Critical patent/KR102168151B1/ko
Priority to CN201380054682.8A priority patent/CN104737072B/zh
Priority to JP2014554374A priority patent/JP5982013B2/ja
Publication of WO2014103867A1 publication Critical patent/WO2014103867A1/ja

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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
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • 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
    • C23C14/0676—Oxynitrides

Definitions

  • the present invention relates to a phase shift mask capable of forming a fine and highly accurate exposure pattern and a manufacturing method thereof, and more particularly to a technique suitable for use in manufacturing a flat panel display.
  • a phase shift mask is used to expose and transfer a fine pattern onto a resist film formed on a substrate made of silicon, glass, or the like.
  • the line width size has been further refined by improving the patterning accuracy, and the image quality has been greatly improved.
  • the gap between the photomask and the substrate during exposure becomes smaller. Since the glass substrate used for the flat panel has a large size exceeding 300 mm, the waviness or surface roughness of the glass substrate becomes a large value, and it is easily affected by the depth of focus.
  • the FPD exposure uses the combined wavelength of g-line (436 nm), h-line (405 nm), and i-line (365 nm), and the same-size proxy proximity exposure method is used. (For example, refer to Patent Document 1).
  • An aspect according to the present invention has been made to solve the above-described problems, and provides a phase shift mask capable of efficiently forming a fine, high-precision exposure pattern with a large area as in FPD manufacturing, and a method for manufacturing the same.
  • the purpose is to do.
  • a method of manufacturing a phase shift mask includes a step of forming a light shielding layer mainly composed of Cr patterned on a transparent substrate; an inert gas, a nitriding gas, and an oxidizing gas Is sputtered with a target of a chromium-based material in an atmosphere of a mixed gas that includes: and a phase difference of about 180 ° with respect to i-line, and the oxidizing gas in the mixed gas is 10.4% or less forming and patterning a phase shift layer mainly composed of Cr capable of setting the difference between the g-line transmittance and the i-line transmittance to 5% or less.
  • a phase shift mask includes a light-shielding layer mainly composed of Cr formed on a transparent substrate; a phase difference of about 180 ° with respect to i-line; A phase shift layer containing Cr as a main component, which can make the difference between the transmittance and the transmittance of the i-line 5% or less.
  • the phase shift mask is formed such that the light shielding layer is formed on the surface of the transparent substrate, the phase shift layer is formed on the light shielding layer, or the transparent substrate Etching mainly comprising at least one metal selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf on the surface.
  • a stopper layer may be formed, and the light shielding layer may be formed on the etching stopper layer.
  • a step of forming a light shielding layer mainly composed of Cr patterned on a transparent substrate, and under an atmosphere of a mixed gas containing an inert gas, a nitriding gas, and an oxidizing gas Sputtering a chromium-based material target gives a phase difference of about 180 ° with respect to the i-line, and reduces the oxidizing gas in the mixed gas to 10.4% or less and the transmittance of the g-line.
  • phase shift mask blank having substantially the same transmittance with respect to any light and a manufacturing method capable of manufacturing the phase shift mask.
  • the phase shift mask blank can be a phase shift mask blank for a photomask used for exposure processing with a composite wavelength including g-line (436 nm), h-line (405 nm), and i-line (365 nm).
  • the light shielding layer mainly composed of Cr formed on the transparent substrate, the phase difference of about 180 ° with respect to the i-line, and the transmittance of the g-line By having a phase shift layer mainly composed of Cr that can make the difference between the transmittance of the h-line and the transmittance of the i-line 5% or less, it has a large area such as an FPD. Even in the object to be processed, high-definition exposure processing can be performed, and the manufacturing cost can be reduced.
  • the light shielding layer is formed on the surface of the transparent substrate, and the phase shift layer is formed on the light shielding layer, or the phase shift layer is formed on the surface of the transparent substrate.
  • An etching stopper layer mainly composed of at least one metal selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf is formed on the phase shift layer;
  • the light shielding layer may be formed of a phase shift mask blank on which the light shielding layer is formed on the etching stopper layer.
  • a phase shift mask blank having a reduced difference in transmittance due to wavelength can be manufactured, so that a defect in an exposure process can be reduced in an object having a large area such as an FPD, and a high definition can be achieved. It is possible to provide a manufacturing method, a phase shift mask blank, and a manufacturing method thereof capable of manufacturing a phase shift mask capable of manufacturing a large object to be processed with a high yield.
  • the production method of the present invention may include a step of patterning the light shielding layer on the transparent substrate.
  • a phase shift layer is formed on the transparent substrate so as to cover the light shielding layer.
  • the phase shift layer has an atmosphere of a mixed gas containing at least an inert gas, a nitriding gas of 40% or more and 90% or less, and an oxidizing gas of 10.4% or less, more preferably 40% or more and 70%. It is formed by sputtering a target of a chromium-based material in an atmosphere of a mixed gas containing the following nitriding gas and 9.2% to 10.4% oxidizing gas.
  • the phase shift layer has a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, and light having a composite wavelength including g-line (436 nm), h-line (405 nm), and i-line (365 nm).
  • the difference between the g-line transmittance, the h-line transmittance, and the i-line transmittance is 5% or less.
  • the formed phase shift layer is patterned into a predetermined shape.
  • the difference between the g-line transmittance, the h-line transmittance, and the i-line transmittance may be 5% or less and have a phase difference of about 180 °. It has a possible phase shift layer. Therefore, according to the phase shift mask, the inversion action of the phase can be achieved by using the composite wavelength including light in the above-mentioned wavelength region, particularly g-line (436 nm), h-line (405 nm), and i-line (365 nm) as exposure light. Thus, a region where the light intensity is minimized can be formed, and the exposure pattern can be made clearer.
  • the difference between the g-line transmittance and the i-line transmittance is more preferably 2.5% or more and 5% or less.
  • phase shift layer is formed of a chromium oxynitride-based material
  • a sputtered film having a desired transmittance and refractive index can be stabilized by using a mixed gas atmosphere containing an oxidizing gas of 10.4% or less. Can be formed. If the oxidizing gas is 9.2% or more, a desired refractive index can be obtained. Therefore, the transmittance of g-line, h-line, and i-line is increased, and the phase shift effect is increased, which is preferable. However, even if the oxidizing gas is less than 9.2%, the transmittance value is low, and the phase shift effect is reduced, but the effect is recognized. It is good if the oxidizing gas is 6.5% or more.
  • the oxidizing gas exceeds 10.4%, the oxygen concentration in the film is too high and the desired transmittance and refractive index cannot be obtained, and oxidation of the target cannot be suppressed and stable sputtering can be performed. It becomes difficult.
  • the nitriding gas is less than 40%, target oxidation cannot be suppressed, and stable sputtering becomes difficult.
  • the nitriding gas exceeds 70%, it is difficult to obtain desired film properties such as transmittance and refractive index.
  • a phase shift layer having a transmittance of 1 to 20% with respect to i-line can be obtained. Even if the transmittance of the i-line is less than 1%, it is possible to obtain the effect of the phase shift layer slightly, and it may be 0.5% or more.
  • the thickness of the phase shift layer can be set to a thickness that gives a phase difference of about 180 ° to the i-line. Furthermore, the above-described phase shift layer may be formed with a thickness capable of giving a phase difference of about 180 ° with respect to the h-line or the g-line.
  • substantially 180 ° means 180 ° or near 180 °, and is, for example, 180 ° ⁇ 10 ° or less.
  • the thickness of the phase shift layer is such that the difference between the g-line transmittance, the h-line transmittance, and the i-line transmittance is 5% or less, and the phase difference applied to the i-line and g
  • the thickness can be set such that the difference from the phase difference applied to the line is 40 ° or less.
  • the mixed gas may further contain an inert gas. Thereby, stable formation of plasma becomes possible. Further, the concentrations of the nitriding gas and the oxidizing gas can be easily adjusted.
  • the FPD manufacturing method using the phase shift mask of the present invention includes a step of forming a photoresist layer on a substrate.
  • a phase shift mask is disposed in proximity to the photoresist layer.
  • the phase shift mask has a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, and transmits the g-line transmittance, the h-line transmittance, and the i-line transmittance.
  • the phase shift layer is made of a chromium oxynitride-based material that can be 5% or less.
  • the photoresist layer irradiates the phase shift mask with light having a composite wavelength including g-line (436 nm), h-line (405 nm), and i-line (365 nm) as light having a composite wavelength of 300 nm to 500 nm. It is exposed with.
  • the difference between the transmittance of the g-line, the transmittance of the h-line, and the transmittance of the i-line is 5% or less, and any of wavelength regions of 300 nm to 500 nm is used. It has a phase shift layer capable of giving a phase difference of 180 ° to light. Therefore, according to the manufacturing method, the pattern accuracy based on the phase shift effect can be improved by using the light in the wavelength region, and a fine and highly accurate pattern can be formed. Thereby, a high-quality flat panel display can be manufactured.
  • light having the composite wavelength light including g-line (436 nm), h-line (405 nm), and i-line (365 nm) can be used.
  • the phase shift mask of the present invention includes a transparent substrate, a light shielding layer, and a phase shift layer.
  • the light shielding layer is formed on the transparent substrate.
  • the phase shift layer is formed around the light-shielding layer, and the difference in transmittance between g-line, h-line, and i-line is 5% or less, and any of composite wavelength regions of 300 nm to 500 nm. It is made of a chromium oxynitride material capable of having a phase difference of 180 ° with respect to the light.
  • phase shift mask it is possible to improve the pattern accuracy based on the phase shift effect by using the light of the composite wavelength, and it is possible to form a fine and highly accurate pattern.
  • the above effect becomes more prominent by using an exposure technique in which light having different wavelengths (for example, g-line (436 nm), h-line (405 nm), i-line (365 nm)) in the wavelength range is combined.
  • the thickness of the phase shift layer is such that the difference in transmittance between g-line, h-line and i-line is 5% or less, and the difference between the phase difference applied to i-line and the phase difference applied to g-line
  • the thickness can be set to 30 ° or less.
  • FIG. 1 is a process diagram schematically showing a method of manufacturing a phase shift mask according to the present embodiment.
  • the phase shift mask of this embodiment is configured as a patterning mask for an FPD glass substrate, for example.
  • a composite wavelength of i-line, h-line and g-line is used for exposure light.
  • a light shielding layer 11 is formed on a transparent substrate 10.
  • the transparent substrate 10 a material excellent in transparency and optical isotropy is used, for example, a quartz glass substrate is used.
  • the size in particular of the transparent substrate 10 is not restrict
  • the present invention can be applied to a substrate having a diameter of about 100 mm, a rectangular substrate having a side of about 50 to 100 mm to a side of 300 mm or more, a quartz substrate having a length of 450 mm, a width of 550 mm, and a thickness of 8 mm. Even a substrate of 1000 mm or more can be used.
  • the surface roughness of the transparent substrate 10 may be reduced by polishing the surface of the transparent substrate 10.
  • the flatness of the transparent substrate 10 can be set to 50 ⁇ m or less, for example. As a result, the depth of focus of the mask is increased, and it is possible to greatly contribute to the formation of a fine and highly accurate pattern.
  • the flatness of the transparent substrate is more preferably 20 ⁇ m or less, and it is preferably 10 ⁇ m or less because the contribution to the formation of a fine and high-definition pattern is further increased.
  • the light shielding layer 11 is made of metal chromium or a chromium compound (hereinafter also referred to as a chromium-based material), but is not limited thereto, and is a metal silicide-based material (for example, MoSi, TaSi, TiSi, WSi) or an oxide thereof. Nitride and oxynitride are applicable.
  • the thickness of the light shielding layer 11 is not particularly limited, and may be a thickness (for example, 80 to 200 nm) at which an optical density equal to or higher than a predetermined value is obtained.
  • an electron beam vapor deposition method As a film forming method, an electron beam vapor deposition method, a laser vapor deposition method, an atomic layer film formation method (ALD method), an ion assist sputtering method, or the like can be applied. Especially in the case of a large substrate, the film thickness is uniform by a DC sputtering method. It is possible to form a film with excellent properties.
  • a photoresist layer 12 is formed on the light shielding layer 11.
  • the photoresist layer 12 may be a positive type or a negative type.
  • a liquid resist is used, but a dry film resist may be used.
  • the photoresist layer 12 is exposed and developed to remove the region 12a and form a resist pattern 12P1 on the light shielding layer 11 (FIG. 1). (C)).
  • the resist pattern 12P1 functions as an etching mask for the light shielding layer 11, and the shape is appropriately determined according to the etching pattern of the light shielding layer 11.
  • the light shielding layer 11 is etched into a predetermined pattern shape.
  • the light shielding layer 11P1 patterned into a predetermined shape is formed on the transparent substrate 10.
  • a wet etching method or a dry etching method can be applied to the etching process of the light shielding layer 11, and in particular, when the substrate 10 is large, an etching process with high in-plane uniformity can be realized by adopting the wet etching method. Become.
  • the etching solution for the light shielding layer 11 can be appropriately selected.
  • the light shielding layer 11 is a chromium-based material, for example, an aqueous solution of ceric ammonium nitrate and perchloric acid can be used. Since this etching solution has a high selection ratio with the glass substrate, the substrate 10 can be protected when the light shielding layer 11 is patterned.
  • the light shielding layer 11 is made of a metal silicide material, for example, ammonium hydrogen fluoride can be used as the etchant.
  • the resist pattern 12P1 is removed as shown in FIG.
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 12P1.
  • the phase shift layer 13 is formed.
  • the phase shift layer 13 is formed on the transparent substrate 10 so as to cover the light shielding layer 11P1.
  • an electron beam (EB) vapor deposition method As a film formation method of the phase shift layer 13, an electron beam (EB) vapor deposition method, a laser vapor deposition method, an atomic layer film formation (ALD) method, an ion assisted sputtering method, or the like can be applied.
  • EB electron beam
  • ALD atomic layer film formation
  • ion assisted sputtering method By adopting the DC sputtering method, it is possible to form a film with excellent film thickness uniformity.
  • the present invention is not limited to the DC sputtering method, and an AC sputtering method or an RF sputtering method may be applied.
  • the phase shift layer 13 is made of a chromium-based material.
  • the phase shift layer 13 is made of chromium nitride oxide.
  • the chromium-based material good patternability can be obtained particularly on a large substrate.
  • metal silicide type materials such as MoSi, TaSi, WSi, CrSi, NiSi, CoSi, ZrSi, NbSi, TiSi, or these compounds, may be used.
  • Al, Ti, Ni, or a compound thereof may be used.
  • phase shift layer 13 made of chromium oxynitride is formed by sputtering
  • a mixed gas of a nitriding gas and an oxidizing gas, or a mixed gas of an inert gas, a nitriding gas, and an oxidizing gas is used as a process gas.
  • the film forming pressure can be set to 0.1 Pa to 0.5 Pa, for example.
  • the inert gas halogen, especially argon can be applied.
  • the oxidizing gas includes CO, CO 2 , NO, N 2 O, NO 2 , O 2 and the like.
  • the nitriding gas includes NO, N 2 O, NO 2 , N 2 and the like.
  • Ar, He, Xe or the like is used as the inert gas, but typically Ar is used.
  • the mixed gas may further contain a carbonizing gas such as CH 4 .
  • the flow rate (concentration) of the nitriding gas and the oxidizing gas in the mixed gas is an important parameter for determining the optical properties (transmittance, refractive index, etc.) of the phase shift layer 13.
  • the mixed gas is adjusted under conditions of a nitriding gas of 40% to 70% and an oxidizing gas of 9.2% to 10.4%. By adjusting the gas conditions, it is possible to optimize the refractive index, transmittance, reflectance, thickness and the like of the phase shift layer 13.
  • the oxygen concentration in the film is too low and the transmittance is too low. Further, when the oxidizing gas exceeds 10.4%, the oxygen concentration in the film is too high, and the variation in transmittance due to the wavelength of light becomes too large, and the oxidation of the target cannot be suppressed and is stable. Sputtering becomes difficult.
  • carbon dioxide can be raised as the oxidizing gas. If the nitriding gas is less than 40%, target oxidation cannot be suppressed, and stable sputtering becomes difficult. On the other hand, if the nitriding gas exceeds 90%, the oxygen concentration in the film is too low and it becomes difficult to obtain a desired refractive index.
  • nitrogen gas can be given as the nitriding gas.
  • a phase shift layer having a transmittance of 1 to 20% with respect to i-line can be obtained.
  • the transmittance may be 0.5% or more.
  • the thickness of the phase shift layer 13 is set to a thickness capable of giving a phase difference of 180 ° to any of g-line, h-line, and i-line light in a wavelength region of 300 nm to 500 nm.
  • the light to which the phase difference of 180 ° is given is inverted in phase, so that the intensity of the light is canceled by the interference action with the light that does not pass through the phase shift layer 13.
  • a region where the light intensity is minimum (for example, zero) is formed, so that the exposure pattern becomes clear and a fine pattern can be formed with high accuracy.
  • the light in the wavelength region is a composite light (polychromatic light) of i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm).
  • the phase shift layer 13 is formed with a thickness that can give a phase difference of 180 °.
  • the light having the target wavelength may be any of i-line, h-line, and g-line, or light in a wavelength region other than these. As the light whose phase is to be inverted has a shorter wavelength, a finer pattern can be formed.
  • the phase shift layer 13 can be formed with a thickness such that the difference between the phase difference applied to the i-line and the phase difference applied to the g-line is 30 ° or less.
  • the phase shift layer can be formed to a film thickness that can give a phase difference of about 180 ° (180 ° ⁇ 10 °) to the h-line that is the intermediate wavelength region of the composite wavelength.
  • a phase difference close to 180 ° can be imparted to any of the i-line and g-line light, and the same phase shift effect can be obtained for each light.
  • the film thickness of the phase shift layer 13 is preferably uniform in the plane of the transparent substrate 10.
  • the phase shift layer 13 is formed with a film thickness difference such that the difference in phase difference in the substrate plane is 20 ° or less for each single wavelength light of g-line, h-line, and i-line. . If the difference in phase difference exceeds 20 °, the intensity of light intensity decreases due to the effect of superimposing the light intensity at the composite wavelength, and the patterning accuracy decreases. By setting the difference of the phase difference to 15 ° or less, further 10 ° or less, the patterning accuracy can be further improved.
  • the transmittance of the phase shift layer 13 can be in the range of 1% to 20% for i-line, for example.
  • the transmittance may be 0.5% or more.
  • the transmittance can be in the range of 2% to 15%. Further, in the above range, the transmittance can be 3% or more and 10% or less.
  • the reflectance of the phase shift layer 13 is 40% or less, for example. Thereby, it is difficult to form a ghost pattern when patterning a substrate to be processed (flat panel substrate or semiconductor substrate) using the phase shift mask, and good pattern accuracy can be ensured.
  • the transmittance and reflectance of the phase shift layer 13 can be arbitrarily adjusted according to the gas conditions during film formation. According to the mixed gas conditions described above, a transmittance of 1% to 20% and a reflectance of 40% or less can be obtained with respect to i-line.
  • the transmittance may be 0.5% or more.
  • the thickness of the phase shift layer 13 can be appropriately set within the range in which the above-described optical characteristics can be obtained.
  • the optical characteristics described above can be obtained by optimizing the thickness of the phase shift layer 13.
  • the film thickness of the phase shift layer 13 that can obtain the optical characteristics depending on the gas conditions is, for example, 100 nm or more and 130 nm or less. In this range, the thickness of the phase shift layer 13 can be in the range of 110 nm to 125 nm.
  • the transmittance for i-line is 3.10. %
  • the phase difference at the i-line can be 180 °
  • the transmittance at the g-line can be 7.95%
  • the phase difference can be 150 °.
  • N 2 was used as the nitriding gas
  • CO 2 was used as the oxidizing gas
  • Ar was used as the inert gas.
  • the film forming pressure was 0.4 Pa.
  • the transmittance for i-line is 3.10% and the phase difference for i-line is 180 °.
  • the transmittance in g-line can be 7.95%.
  • the phase shift layer with a thickness that can give a phase difference of 180 ° ⁇ 10 ° to the i-line, the difference in transmittance between the i-line, the h-line, and the g-line is reduced to 5% or less. Can be suppressed.
  • the transmittance of i-line can be set in the range of 1% to 10%.
  • a photoresist layer 14 is formed on the phase shift layer 13.
  • the photoresist layer 14 may be a positive type or a negative type.
  • the photoresist layer 14 is exposed and developed to form a resist pattern 14P1 on the phase shift layer 13.
  • the resist pattern 14 ⁇ / b> P ⁇ b> 1 functions as an etching mask for the phase shift layer 13, and the shape is appropriately determined according to the etching pattern for the phase shift layer 13.
  • the phase shift layer 13 is etched into a predetermined pattern shape.
  • the phase shift layer 13P1 patterned in a predetermined shape is formed on the transparent substrate 10.
  • a wet etching method or a dry etching method can be applied to the etching process of the phase shift layer 13, and when the substrate 10 is large, an etching process with high in-plane uniformity can be realized by adopting the wet etching method. It becomes.
  • the etching solution for the phase shift layer 13 can be appropriately selected.
  • an aqueous solution of ceric ammonium nitrate and perchloric acid can be used. Since this etching solution has a high selectivity with respect to the glass substrate, the substrate 10 can be protected when the phase shift layer 13 is patterned.
  • the resist pattern 14P1 is removed as shown in FIG.
  • a sodium hydroxide aqueous solution can be used to remove the resist pattern 14P1.
  • the phase shift mask 1 is manufactured.
  • the phase shift layer 13P1 having the above-described configuration is formed around the light shielding layer pattern 11P1.
  • the i-line, h-line, and g-line the difference in transmittance between them can be suppressed to 5% or less, and the pattern accuracy based on the phase shift effect can be improved, so that a fine and highly accurate pattern can be formed.
  • a photoresist layer is formed on the surface of the glass substrate on which the insulating layer and the wiring layer are formed.
  • a spin coater is used to form the photoresist layer.
  • the photoresist layer is subjected to a heating (baking) process and then subjected to an exposure process using the phase shift mask 1.
  • the phase shift mask 1 is disposed in the vicinity of the photoresist layer.
  • the surface of the glass substrate is irradiated with a composite wavelength including g-line (436 nm), h-line (405 nm), and i-line (365 nm) of 300 nm to 500 nm through the phase shift mask 1.
  • composite light of g-line, h-line, and i-line is used as the light of the composite wavelength.
  • the phase shift mask 1 suppresses the difference in transmittance between the i-line, the h-line, and the g-line to 5% or less, and applies any light in a wavelength region of 300 nm to 500 nm.
  • the phase shift layer 13P1 capable of giving a phase difference of 180 ° is provided. Therefore, according to the manufacturing method, since the pattern accuracy based on the phase shift effect can be improved by using the light in the wavelength region, and the depth of focus can be increased, a fine and highly accurate pattern can be obtained. Formation is possible. Thereby, a high-quality flat panel display can be manufactured.
  • FIG. 4 is a process diagram for explaining a method of manufacturing a phase shift mask according to the second embodiment of the present invention.
  • portions corresponding to those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the phase shift mask 2 (FIG. 4 (J)) of the present embodiment has an alignment mark for alignment at the periphery, and this alignment mark is formed by the light shielding layer 11P2.
  • this alignment mark is formed by the light shielding layer 11P2.
  • the light shielding layer 11 is formed on the transparent substrate 10 (FIG. 4A).
  • a photoresist layer 12 is formed on the light shielding layer 11 (FIG. 4B).
  • the photoresist layer 12 may be a positive type or a negative type.
  • a resist pattern 12P2 is formed on the light shielding layer 11 (FIG. 4C).
  • the resist pattern 12P2 functions as an etching mask for the light shielding layer 11, and the shape is appropriately determined according to the etching pattern of the light shielding layer 11.
  • FIG. 4C shows an example in which a resist pattern 12P2 is formed so as to leave the light shielding layer over a predetermined range on the periphery of the substrate 10.
  • the light shielding layer 11 is etched into a predetermined pattern shape.
  • the light shielding layer 11P2 patterned in a predetermined shape is formed on the transparent substrate 10 (FIG. 4D).
  • the resist pattern 12P2 is removed (FIG. 4E).
  • an aqueous sodium hydroxide solution can be used to remove the resist pattern 12P2.
  • the phase shift layer 13 is formed.
  • the phase shift layer 13 is formed on the transparent substrate 10 so as to cover the light shielding layer 11P2 (FIG. 4F).
  • the phase shift layer 13 is made of a chromium oxynitride material and is formed by a DC sputtering method.
  • a mixed gas of a nitriding gas and an oxidizing gas, or a mixed gas of an inert gas, a nitriding gas, and an oxidizing gas can be used as the process gas.
  • the phase shift layer 13 is formed under the same film formation conditions as in the first embodiment described above.
  • a photoresist layer 14 is formed on the phase shift layer 13 (FIG. 4G).
  • a resist pattern 14P2 is formed on the phase shift layer 13 (FIG. 4H).
  • the resist pattern 14P2 functions as an etching mask for the phase shift layer 13, and the shape is appropriately determined according to the etching pattern for the phase shift layer 13.
  • phase shift layer 13 is etched into a predetermined pattern shape.
  • the phase shift layer 13P2 patterned in a predetermined shape is formed on the transparent substrate 10 (FIG. 4I).
  • the resist pattern 14P2 is removed (FIG. 4J).
  • a sodium hydroxide aqueous solution can be used to remove the resist pattern 14P2.
  • the phase shift mask 2 according to this embodiment is manufactured. According to the phase shift mask 2 of the present embodiment, since the alignment mark is formed of the light shielding layer 11P2, the alignment mark can be easily recognized optically, and high-accuracy alignment is possible. This embodiment can be implemented in combination with the first embodiment described above.
  • phase shift layer 13 can function as a halftone layer (semi-transmissive layer). In this case, it is possible to make a difference in exposure amount between light transmitted through the phase shift layer 13 and light not transmitted.
  • the phase shift layer is formed and patterned after the light shielding layer is patterned.
  • the present invention is not limited to this.
  • the light shielding layer is formed. Films and patterning may be performed. That is, it is possible to change the stacking order of the light shielding layer and the phase shift layer.
  • the etching (not shown) whose main component is at least one metal selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf is provided between the light shielding layer and the phase shift layer.
  • a stopper layer is preferably provided.
  • the light shielding layer 11P1 is formed by etching a necessary portion. Instead, the formation region of the light shielding layer 11P1 is opened. After the resist pattern to be formed is formed, the light shielding layer 11 may be formed. After the formation of the light shielding layer 11, the light shielding layer 11P1 can be formed in a necessary region by removing the resist pattern (lift-off method).
  • Phase shift mask 10 Transparent substrate 11, 11P1 ... Light shielding layer 12P1, 14P1 ... Resist pattern 13P1 ... Phase shift layer

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
PCT/JP2013/084059 2012-12-27 2013-12-19 位相シフトマスクおよびその製造方法 WO2014103867A1 (ja)

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CN201380054682.8A CN104737072B (zh) 2012-12-27 2013-12-19 相移掩膜及其制造方法
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JP2018116269A (ja) * 2017-01-18 2018-07-26 Hoya株式会社 表示装置製造用の位相シフトマスクブランク、表示装置製造用の位相シフトマスクの製造方法、並びに表示装置の製造方法
JP2019204137A (ja) * 2019-09-10 2019-11-28 Hoya株式会社 フォトマスクの設計方法および製造方法、並びに表示装置の製造方法

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JP6767735B2 (ja) * 2015-06-30 2020-10-14 Hoya株式会社 フォトマスク、フォトマスクの設計方法、フォトマスクブランク、および表示装置の製造方法
JP6259508B1 (ja) * 2016-12-28 2018-01-10 株式会社エスケーエレクトロニクス ハーフトーンマスク、フォトマスクブランクス及びハーフトーンマスクの製造方法
KR20210099922A (ko) 2020-02-05 2021-08-13 정현서 바이오헬스 기술을 이용한 스마트 글래스

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CN104737072B (zh) 2020-01-07
JP5982013B2 (ja) 2016-08-31
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CN104737072A (zh) 2015-06-24
TWI592738B (zh) 2017-07-21
KR102168151B1 (ko) 2020-10-20

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