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WO2014171512A1 - 位相シフトマスクの製造方法および位相シフトマスク - Google Patents

位相シフトマスクの製造方法および位相シフトマスク Download PDF

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Publication number
WO2014171512A1
WO2014171512A1 PCT/JP2014/060935 JP2014060935W WO2014171512A1 WO 2014171512 A1 WO2014171512 A1 WO 2014171512A1 JP 2014060935 W JP2014060935 W JP 2014060935W WO 2014171512 A1 WO2014171512 A1 WO 2014171512A1
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WIPO (PCT)
Prior art keywords
phase shift
layer
pattern
thickness
region
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PCT/JP2014/060935
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English (en)
French (fr)
Japanese (ja)
Inventor
聖 望月
中村　大介
良紀 小林
影山　景弘
Original Assignee
アルバック成膜株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=51731448&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014171512(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
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 CN201480005621.7A priority Critical patent/CN104937490B/zh
Priority to KR1020157018176A priority patent/KR101760337B1/ko
Priority to JP2015512521A priority patent/JP5948495B2/ja
Publication of WO2014171512A1 publication Critical patent/WO2014171512A1/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
    • G03F1/28—Phase shift masks [PSM]; PSM blanks; Preparation thereof with three or more diverse phases on the same PSM; 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
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/29—Rim PSM or outrigger PSM; 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
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching

Definitions

  • the present invention relates to a method of manufacturing a phase shift mask and a phase shift mask capable of forming a fine and highly accurate exposure pattern.
  • the present invention relates to a technique used for manufacturing a flat panel display.
  • phase shift mask that can form a finer pattern using a single wavelength by using light interference at a pattern edge from a photomask having a light shielding film pattern formed using a composite wavelength in order to perform pattern miniaturization in the photomask.
  • Patent Document 1 an edge-enhanced phase shift mask using an i-line single wavelength is used as shown in Patent Document 1, but for further miniaturization, Patent Document 2 As shown in FIG. 1, a semi-transmission type phase shift mask has been used in which the exposure wavelength is shortened to a single ArF wavelength.
  • Patterns are also formed by exposure with an exposure wavelength that is a composite wavelength of g-line, h-line, and i-line. It has been broken. Recently, in order to form a high-definition screen even in the above flat panel display, the pattern profile has been further miniaturized. Thus, edge-enhanced phase shift masks have been used.
  • Edge-enhanced phase shift masks for flat panels are exposed in the composite wavelength region, and there is a problem that the phase shift effect is not sufficient at wavelengths other than the phase shift effect.
  • the resulting phase shift mask was in a desired situation.
  • the phase shift film is formed after patterning the light shielding film, and the phase shift film is patterned.
  • There is an underlay type phase shift mask in which an etch stop film and a light-shielding film are sequentially formed from a substrate, and are sequentially patterned.
  • the lower type phase shift mask has the same problem
  • the single layer type phase shift mask made of a semi-transmissive film made of a phase shift layer has the same problem.
  • the phase shift pattern formed with a predetermined thickness is sagged, that is, The pattern line width (width dimension) is different from the shape where the thickness reduction degree is set, and as a result, the portion where the light intensity depending on the thickness of the phase shift layer becomes zero differs from the desired state. ) Is unfavorable because it may reduce the high definition as a mask.
  • exposure in the composite wavelength region is used when forming flat panel patterns, but there is a limit to the formation of further fine patterns because the phase shift effect utilizing all the composite wavelengths cannot be obtained. In the exposure in the composite wavelength region, a process for sufficiently miniaturizing by sufficiently exhibiting the phase shift effect has been desired.
  • the aspect of the present invention is suitably used for manufacturing a flat panel display, can form a fine and highly accurate exposure pattern, can apply a composite wavelength, and more efficiently exhibits a phase shift effect.
  • An object of the present invention is to provide a method of manufacturing a phase shift mask and a phase shift mask.
  • a method of manufacturing a phase shift mask according to an aspect of the present invention includes a transparent substrate, A phase shift capable of providing a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, mainly composed of Cr having a portion formed with a constant thickness on the surface of the transparent substrate.
  • the etching rate of each stage in the phase shift layer can be set by setting the flow rate ratio of the oxidizing gas in the deposition atmosphere gas.
  • the thickness of each stage can correspond so as to have a phase difference of 180 ° for light of different wavelengths.
  • a film forming gas as a film forming atmosphere of each stage in the phase shift layer includes an inert gas, a nitriding gas, and an oxidizing gas, or includes a nitriding gas and an oxidizing gas, and the total gas flow rate
  • the flow rate ratio of the oxidizing gas is selected from the range of 3.68% to 24.89%, and The ratio of the oxidizing gas to the total gas flow rate for each layer may be different.
  • Have or even A phase shift layer is formed on the transparent substrate, and at least one metal selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf is mainly formed on the phase shift layer. It may be formed through an etch stopper layer as a component, forming a light shielding layer on the etch stopper layer, and forming a phase shift pattern by pattern formation.
  • a phase shift mask according to another aspect of the present invention is produced by any one of the production methods described above, A transparent substrate; A phase shift capable of providing a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, mainly composed of Cr having a portion formed with a constant thickness on the surface of the transparent substrate.
  • the thickness of each stage can correspond so that light of different wavelengths has a phase difference.
  • the phase shift layer has a multi-step region thickness of 180 ° for g-line, h-line, and i-line, or the multi-step region thickness of the phase-shift layer has a phase difference of 180 ° for h-line and i-line. It is possible to adopt means having The wavelength set to have a phase difference of 180 ° can be set so as to include g-line, h-line, and i-line as described above, but does not include g-line, and includes h-line and i-line. It is also possible to set to include.
  • a method of manufacturing a phase shift mask according to another aspect of the present invention includes a transparent substrate, A phase shift capable of providing a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, mainly composed of Cr having a portion formed with a constant thickness on the surface of the transparent substrate.
  • the phase shift layer In the boundary portion between the phase shift layer and the transparent substrate, by forming a multistage region in which the thickness change of the phase shift layer is set in multiple stages, at least in the single layer portion of the phase shift pattern on the transparent substrate, By forming a multi-stage area where the thickness change is set in multiple stages so that the thickness decreases toward the exposed transparent substrate surface, the light intensity at each predetermined wavelength light used for exposure is reduced to zero. A portion corresponding to a certain thickness is formed with a predetermined width dimension along the outline of the phase shift pattern.
  • the portion corresponding to the thickness corresponding to the light having the composite wavelength in the above wavelength region is formed with a predetermined width dimension as if it were similar to the outline of the phase shift pattern,
  • each thickness dimension corresponding to each adaptive wavelength in the composite wavelength in the above-described wavelength range in exposure is maintained in the width direction in each stage of the multistage region, so that each of these stages is It becomes possible to have a predetermined width in which the light intensity is zero corresponding to a predetermined wavelength among the composite wavelengths.
  • the composite wavelength in the above-mentioned wavelength range can be used for exposure at the same time, and the phase shift effect can be surely achieved. Therefore, it is possible to further improve the definition, shorten the exposure time, and improve the exposure efficiency. It is possible to manufacture a simple phase shift mask.
  • the etching rate of each stage in the phase shift layer can be set by setting the flow rate ratio of the oxidizing gas in the film forming atmosphere gas, and the plan view is obtained.
  • the boundary portion between the phase shift layer and the transparent substrate forming a multistage region in which the thickness change of the phase shift layer is set in multiple stages, at least in a single layer portion of the phase shift pattern on the transparent substrate It is possible to form a multistage region in which the thickness change is set in multiple stages so that the thickness decreases toward the transparent substrate surface.
  • the thickness of each step corresponds to a phase difference of 180 ° for light of different wavelengths, so that each step corresponds to a predetermined wavelength of the composite wavelength. It is possible to have a predetermined width that is zero. Therefore, the light intensity can be made zero at each wavelength, and it becomes easy to cope with high definition.
  • a film forming gas as a film forming atmosphere of each stage in the phase shift layer includes an inert gas, a nitriding gas and an oxidizing gas, or a nitriding gas and an oxidizing gas, and an oxidizing gas with respect to the total gas flow rate.
  • the film thickness state in the multistage region can be controlled to a desired state.
  • the film thickness is controlled so that the film thickness of each stage of the multistage region corresponds to the thickness at which the light intensity becomes zero in the light of the composite wavelength in the above wavelength range, and the composite in the above wavelength range. Wavelengths can be used for exposure simultaneously.
  • phase shift layer is formed on the transparent substrate, and the main component is at least one metal selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W, and Hf on the phase shift layer. And forming a phase shift pattern by pattern formation by forming a light shielding layer on the etching stopper layer and thereby forming a phase shift pattern in the exposure region.
  • Phase shift mask consisting of a single layer, phase shift layer is located on the upper side, so-called top-type phase shift mask with the light shielding layer located on the lower side, phase shift layer is located on the lower side, and etching is performed on the upper side
  • phase shift layer is located on the lower side
  • etching is performed on the upper side
  • the boundary portion including the multistage region is formed of a single phase shift layer.
  • a phase shift mask according to another aspect of the present invention is produced by any one of the production methods described above, A transparent substrate; A phase shift capable of providing a phase difference of 180 ° with respect to any light in a wavelength region of 300 nm or more and 500 nm or less, mainly composed of Cr having a portion formed with a constant thickness on the surface of the transparent substrate.
  • a phase shift mask having a layer The phase shift layer is formed with a phase shift pattern having a boundary portion in plan view with the transparent substrate, In the boundary portion between the phase shift layer and the transparent substrate in plan view, by having a multistage region in which the thickness of the phase shift layer is changed in multiple stages, at least in a single layer portion of the phase shift pattern on the transparent substrate.
  • the location where the multi-step area where the thickness change is set in multiple steps so that the thickness decreases toward the exposed transparent substrate surface corresponds to the thickness at which the light intensity becomes zero for each predetermined wavelength of light used for exposure.
  • the portion corresponding to the thickness corresponding to the light having the composite wavelength in the above wavelength region is formed with a predetermined width dimension as if it were similar to the outline of the phase shift pattern, With respect to the thickness dimension corresponding to each adaptive wavelength in the composite wavelength in the above-mentioned wavelength range in exposure, each thickness dimension is maintained in the width direction in each stage of the multistage region. Since it becomes possible to have a predetermined width corresponding to the predetermined wavelength, the light intensity is zero, so that the composite wavelength in the above wavelength range can be used for exposure at the same time, and the phase shift effect can be surely achieved. It is possible to manufacture a phase shift mask capable of improving the exposure efficiency such as higher definition, shorter exposure time, and higher exposure energy.
  • the thickness of each step corresponds so that light of different wavelengths has a phase difference, so that the composite wavelength in the above-mentioned wavelength range can be used for exposure at the same time to ensure the phase shift effect. Therefore, it is possible to manufacture a phase shift mask capable of improving the exposure efficiency such as higher definition, shorter exposure time, and higher exposure energy.
  • the multi-stage region thickness of the phase shift layer can have a phase difference of 180 ° in g-line, h-line, and i-line, and the multi-stage of the phase-shift layer corresponding to the point where the light intensity is zero in the composite wavelength light
  • Each step thickness in the region can be set to 145.0 nm, 133.0 nm, and 120.0 nm corresponding to the g-line, h-line, and i-line.
  • the film thickness at each stage is not limited to the above values, and a phase difference of 180 ° can be obtained in the range of 140 to 150 nm, 128 to 138 nm, and 115 to 125 nm.
  • phase shift mask which concerns on 1st Embodiment of this invention. It is process drawing explaining the manufacturing process of the phase shift mask which concerns on 1st Embodiment of this invention. It is process drawing explaining the phase shift layer manufacturing process in the manufacturing process of the phase shift mask which concerns on 1st Embodiment of this invention. It is process drawing explaining the phase shift layer manufacturing process in the manufacturing process of the phase shift mask which concerns on 1st Embodiment of this invention. It is a schematic cross section which shows the phase shift mask which concerns on 2nd Embodiment of this invention. It is process drawing explaining the manufacturing process of the phase shift mask which concerns on 2nd Embodiment of this invention. It is a schematic cross section which shows the phase shift mask which concerns on 3rd Embodiment of this invention. It is process drawing explaining the manufacturing process of the phase shift mask which concerns on 3rd Embodiment of this invention.
  • FIG. 1 is a schematic cross-sectional view (a) showing a phase shift mask according to the present embodiment and an enlarged view (b) showing a multistage region.
  • M1 is a phase shift mask.
  • the phase shift mask M1 of the present embodiment is provided on the surface of a glass substrate (transparent substrate) S, and is a phase shift composed of a single phase shift layer 11 capable of having a phase difference of 180 °. It has a pattern 11a.
  • it is configured as a patterning mask for an FPD glass substrate.
  • a composite wavelength of i-line, h-line and g-line is used for exposure light.
  • the phase shift mask M1 has a thickness of the phase shift pattern 11a at the boundary portion B1 between the portion C where the glass substrate S is exposed in plan view and the formed phase shift pattern 11a in the exposure region where the exposure pattern is formed.
  • the phase shift pattern 11a is formed in multiple layers by laminating layers having different etching rates, refractive indexes, transmittances, reflectances, etc., and the step portions of the uniform region B1a and the multi-step region B1b with respect to the thickness of this layer configuration. The shape corresponds.
  • the transparent substrate S a material excellent in transparency and optical isotropy is used.
  • a quartz glass substrate can be used.
  • size in particular of the transparent substrate S 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, and further, a quartz substrate having a length of 450 mm, a width of 550 mm, and a thickness of 8 mm, A substrate having a thickness of 1000 mm or more and a thickness of 10 mm or more can also be used.
  • the flatness of the transparent substrate S may be improved by polishing the surface of the transparent substrate S.
  • the flatness of the transparent substrate S can be set to 20 ⁇ 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. Further, the flatness is preferably as small as 10 ⁇ m or less.
  • the phase shift layer 11 is mainly composed of Cr, and is specifically selected from Cr alone, and oxides, nitrides, carbides, oxynitrides, carbonitrides, and oxycarbonitrides of Cr. It can be composed of one. In addition, two or more kinds selected from these can be laminated.
  • the phase shift layer 11 is formed in multiple layers by laminating layers having different etching rates, refractive indexes, transmittances, and reflectances. Corresponding to the thickness of this layer structure, the step shape of the uniform region B1a and the multi-step region B1b is formed.
  • the phase shift layer 11 has a phase difference of approximately 180 ° with respect to any light in a wavelength region of 300 nm to 500 nm (for example, g-line having a wavelength of 436 nm, h-line having a wavelength of 405 nm, and i-line having a wavelength of 365 nm). It is formed with a possible thickness (for example, 90 to 170 nm).
  • the phase shift layer 11 can be formed by, for example, a sputtering method, an electron beam evaporation method, a laser evaporation method, an ALD method, or the like.
  • the thickness T11 in the uniform thickness region B1a is made equal to the thickness of the phase shift pattern 11a other than the boundary portion B1, and the light intensity corresponding to the g-line is zero.
  • the value corresponds to the thickness Tg (for example, 145.0 nm).
  • the thickness T11 of the uniform region B1a in the phase shift layer 11 can be set to a value larger than Tg, and the thickness corresponding to Th and Ti can correspond to the multistage region B1b.
  • the phase shift pattern 11a has a uniform region B1a, and a step portion B1bh and a step portion B1bi whose thickness decreases toward the exposed portion C in the multi-step region B1b.
  • the multistage region B1b has a width dimension that is an exposed portion C (a portion where the thickness of the phase shift layer is zero and the glass substrate S is exposed) from the end 11t of the thickness T11 of the uniform region B1a. Up to the end 11u.
  • a stepped portion B1bh and a stepped portion B1bi having different thickness dimensions are provided in the direction in which the thickness decreases.
  • the multi-step region B1b includes a step portion B1bh having a thickness Th (for example, 133.0 nm) at which the h line has a phase difference of 180 ° and the light intensity becomes zero, and a thickness at which the light intensity corresponding to the i line becomes zero. And a step portion B1bi having Ti (for example, 120.0 nm).
  • the thickness Tg is from the end portion 11t to the end portion 11t of the uniform thickness region (uniform region) B1a, and the step portion B1bh from the end portion 11t to the end portion 11sh is the thickness Th.
  • the thickness state of the multi-step region B1b is set so that the step portion B1bi from 11sh to the end portion 11si has the thickness Ti.
  • the ratio of the distance B1b in which the thickness decreases with respect to the thickness T11 of the phase shift pattern 11a is ⁇ 3 ⁇ B1b / T11 ⁇ 3.
  • the distance B1b in which the thickness decreases in the multistage area B1b is the width dimension of the multistage area B1b in plan view. 1A and 1B
  • the distance B1b is from the end portion 11t of the thickness T11 of the phase shift pattern 11a to the end portion 11u of the zero thickness, and from the uniform thickness region B1a to the glass substrate S.
  • the direction toward the exposed portion C is positive, and the direction opposite to the direction toward the exposed portion C of the glass substrate S from the end portion 11t of the thickness T11 of the phase shift pattern 11a is negative.
  • FIGS. 1A and 1B the case of going to the right side from the end 11t is positive, and the case of going to the left side is negative.
  • phase shift mask M1 by using a 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, the phase inversion action
  • the pattern contour is formed so that the light intensity is minimized, and the exposure pattern can be made clearer.
  • the phase shift effect can be obtained at any wavelength with respect to the light having these broad composite wavelengths. As a result, the pattern accuracy is greatly improved, and a fine and highly accurate pattern can be formed.
  • the phase shift layer can be formed of, for example, a chromium oxynitride chromium carbide material, and the thickness of the phase shift layer has a thickness that gives a phase difference of about 180 ° simultaneously to the i-line, h-line, or g-line. It can be formed along the pattern contour shape.
  • “approximately 180 °” means 180 ° or near 180 °, for example, 180 ° ⁇ 10 ° or less, or 180 ° ⁇ 5 ° or less.
  • this phase shift mask it is possible to improve the pattern accuracy based on the phase shift effect by using the light in the wavelength region, and it is possible to form a fine and highly accurate pattern. Thereby, a high-quality flat panel display can be manufactured.
  • the phase shift mask of the present embodiment can be 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.
  • FIG. 2 is a process chart schematically showing the outline of the method for manufacturing a phase shift mask according to the present embodiment
  • FIG. 3 is a process chart showing the method for manufacturing a phase shift layer.
  • the phase shift mask M1 of the present embodiment has alignment marks for alignment on the outer periphery of the exposure area, and the alignment marks are formed of a light shielding layer 13a. .
  • a light shielding layer is formed here for the alignment mark, even a semi-transmissive film made of a phase shift layer without a light shielding layer can function as an alignment mark.
  • a light shielding layer 13 containing Cr as a main component is formed on a glass substrate S.
  • a photoresist layer 14 is formed on the light shielding layer 13.
  • the photoresist layer 14 may be a positive type or a negative type.
  • a resist pattern 14 a is formed on the light shielding layer 13 by exposing and developing the photoresist layer 14.
  • the resist pattern 14 a functions as an etching mask for the light shielding layer 13, and the shape is appropriately determined according to the etching pattern of the light shielding layer 13.
  • FIG. 2C shows an example in which a resist pattern 14a is formed so as to leave the light shielding layer over a predetermined range of the periphery of the glass substrate S.
  • a liquid resist is used as the photoresist layer 14.
  • the light shielding layer 13 is wet etched using the first etching solution over the resist pattern 14a.
  • the first etching solution an etching solution containing cerium diammonium nitrate can be used.
  • cerium diammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
  • the light shielding layer 13a patterned in a predetermined shape is formed on the glass substrate S.
  • the resist pattern 14a is removed as shown in FIG.
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 14a.
  • the phase shift layer 11 is formed.
  • the phase shift layer 11 is formed on the glass substrate S so as to cover the light shielding layer 13a, as shown in FIG.
  • a step B1bh having a thickness Th and a step B1bi having a thickness Ti in a uniform region B1a, a multi-step region B1b can be formed, and a plurality of layers having different etching rates are stacked.
  • the phase shift layer 11 is made of, for example, a chromium oxynitride chromium carbide material, and is formed by a DC sputtering method.
  • a mixed gas of an inert gas, a nitriding gas, and an oxidizing gas, or a mixed gas of a nitriding gas and an oxidizing gas can be used as the 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 CO, CO 2 , NO, N 2 O, NO 2 , O 2 or the like can be used.
  • nitriding gas NO, N 2 O, NO 2 , N 2 or the like can be used.
  • Ar, He, or Xe can be used as the inert gas.
  • Ar is used as the inert gas.
  • the mixed gas may further contain a carbonizing gas such as CH 4 .
  • the phase shift layer 11 is formed in multiple layers by laminating layers having different etching rates, and is formed so as to form a multistage region B1b by controlling the side slope formation by etching as will be described later. Is done. For this reason, the etching rate and optical properties (transmittance, refractive index, etc.) of the phase shift layer 11 are determined using the flow rates (concentrations) of the nitriding gas and the oxidizing gas in the mixed gas as important parameters. By adjusting the gas conditions during film formation, the etching rate of each layer in the phase shift layer 11 can be optimized. Here, carbon dioxide can be raised as the oxidizing gas. As will be described later, the phase shift layer 11 can be laminated as at least three layers, five layers, or more layers corresponding to the uniform region B1a, the stepped portion B1bh, and the stepped portion B1bi.
  • the thickness T11 in the uniform region B1a of the phase shift layer 11 can have a phase difference of 180 ° with respect to the g-line, h-line, and i-line in the wavelength region of 300 nm to 500 nm in the end region B1. Thickness.
  • 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 11.
  • 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 phase shift layer 11 can set the thickness of each layer corresponding to the uniform region B1a having a thickness Tg, the step B1bh having a thickness Th, and the step B1bi having a thickness Ti. it can.
  • 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 11 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.
  • a finer pattern can be formed.
  • the film thickness of the phase shift layer 11 is preferably at least uniform in the exposure area other than the boundary portion B1 in the plane of the transparent substrate S.
  • the reflectance of the phase shift layer 11 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 11 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 uniform region B1a As a film forming condition of the phase shift layer 11 formed in multiple stages, when the respective stages are formed, by setting the flow rate ratio of the oxidizing gas in each film forming atmosphere gas, the uniform region B1a The shapes of the end portions and the multistage region B1b are set.
  • the etching state at each step of the phase shift layer 11 is controlled to control the uniform region B 1 a, step B 1 bh, step B 1 bi,
  • the shape of the multistage region B1b is set so as to have
  • the film forming gas as each film forming atmosphere is an inert gas, a nitriding gas and an oxidizing gas, or a nitriding gas.
  • the flow rate ratio of the oxidizing gas is selected from the range of 3.68 to 24.89% with respect to the total gas flow rate, and the phase shift is achieved by reducing the flow rate ratio of the oxidizing gas.
  • the inclination of the side surfaces of the uniform region B1a, step B1bh, and step B1bi in the pattern 11a and increasing the flow rate ratio of the oxidizing gas the inclination of the side surfaces of the step B1bh and the step B1bi is reduced. . In this way, the inclined region can be set by changing the oxidizing gas for each layer.
  • the state of inclination of the side surfaces of the uniform region B1a, the stepped portion B1bh, and the stepped portion B1bi can be controlled at the time of etching, depending on the flow rate ratio of the oxidizing gas.
  • the composite film thickness including g-line (436 nm), h-line (405 nm), and i-line (365 nm) is used as exposure light by controlling the laminated film thickness of the corresponding multilayer film, the light intensity by the phase inversion action
  • the pattern contour is formed so as to be minimized, and the uniform region B1a of the boundary portion B1 is formed so as to have the width dimension and the thickness dimension of the uniform region B1a, the step portion B1bh, and the step portion B1bi that make the exposure pattern clearer.
  • the shape of the multistage region B1b can be set.
  • the deposition pressure is 0.4 Pa
  • the degree of decrease in the film thickness is controlled so that the thickness of the inclined region has a plurality of points corresponding to the thickness at which the light intensity becomes zero in the light of the composite wavelength in the wavelength range described above.
  • a range of complex wavelengths can be used for exposure simultaneously.
  • a photoresist layer 14 is formed on the phase shift layer 11.
  • the photoresist layer 14 is exposed and developed to form a resist pattern 14 a on the phase shift layer 11.
  • the resist pattern 14 a functions as an etching mask for the phase shift layer 11, and the shape is appropriately determined according to the etching pattern of the phase shift layer 11.
  • phase shift layer 11 is etched into a predetermined pattern shape.
  • the phase shift pattern 11a patterned in a predetermined shape and the exposed portion C of the glass substrate S are formed on the glass substrate S.
  • phase shift pattern 11a having the multistage region B1b by etching the phase shift layer 11 will be described in more detail.
  • a photoresist layer 14 is formed on the phase shift layer 11 which is a multilayer film.
  • a lower layer 11d corresponding to the step portion B1bi, an intermediate layer 11c corresponding to the step portion B1bh, and an upper layer 11b corresponding to the uniform region B1a are laminated from the substrate S side.
  • the lower layer 11d has a thickness Ti so as to correspond to the stepped portion B1bi, and has the smallest etching rate among these three layers.
  • the middle layer 11c has a thickness (Th-Ti) so as to correspond to the stepped portion B1bh, and has an etching rate larger than that of the lower layer 11d.
  • the upper layer 1b has a thickness (Tg ⁇ Th) and a higher etching rate than the middle layer 11c.
  • the etching rates of the lower layer 11d, the middle layer 11c, and the upper layer 11b are set in accordance with the inclined shape of the side surfaces and the width dimension B1bh and the width dimension B1bi of the step.
  • the photoresist layer 14 is exposed and developed to form a resist pattern 14a.
  • the portion of the phase shift layer 11 from which the photoresist layer 14 has been removed as the resist pattern 14a is exposed to an etching solution, whereby the upper layer 11b of this portion is etched, and as shown in FIG. 11b1, 11c1, and 11d1 are simultaneously formed as planar contour shapes along the resist pattern 14a in plan view.
  • the resist pattern 14a is removed as shown in FIGS. 3 (d) and 2 (j).
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 14a.
  • the distance B1bh and the distance B1bi where the thickness in the multistage region B1b in the boundary portion B1 decreases in a multistage manner from the constant value T11 are controlled by the flow rate ratio of the oxidizing gas.
  • the contour of the phase shift pattern 11a can be formed in a multistage shape having a predetermined width dimension, so that the light intensity is zero in the light of the composite wavelength of i-line, h-line, and g-line.
  • a boundary portion B1 having a uniform region B1a, a stepped portion B1bh, and a stepped portion B1bi can be formed. That is, the line width of the phase shift pattern 11a, that is, the line width of the mask can be set more accurately. Thereby, it is possible to manufacture a mask by wet processing with higher definition.
  • phase shift mask M1 a method for manufacturing a flat panel display using the phase shift mask M1 according to the present embodiment will be described.
  • 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 M1.
  • the phase shift mask M1 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 M1.
  • composite light of g-line, h-line, and i-line is used as the light of the composite wavelength.
  • the phase shift mask M1 includes the phase shift layer 11a capable of giving a 180 ° phase difference to the composite light in the wavelength region of 300 nm to 500 nm. Therefore, according to the above manufacturing method, it is possible to improve the pattern accuracy based on the phase shift effect by using the light in the above wavelength region, to further increase the depth of focus, and to increase the light interference and reduce the light. Since it is possible to obtain a region having an intensity of 0 or close to 0, it is possible to form a fine and highly accurate pattern. Thereby, a high-quality flat panel display can be manufactured.
  • the pattern width shift is 30% or more with respect to the target line width (2 ⁇ 0.5 ⁇ m). Although it occurred, it was confirmed that when the exposure was performed using the phase shift mask M1 of the present embodiment, the shift was suppressed to about 7%. In addition, the exposure energy efficiency could be improved by 15%.
  • phase shift pattern 11a having the multi-stage region B1b by etching as the phase shift layer 11 of the present embodiment will be described in more detail.
  • phase shift layer 11 is five.
  • a lower layer 11i, a lower hard layer 11h, an intermediate layer 11g, an intermediate hard layer 11f, and an upper layer 11e are stacked from the substrate S side.
  • a photoresist layer 14 is formed on the phase shift layer 11 that is a multilayer film.
  • the lower layer 11i and the lower hard layer 11h correspond to the step B1bi
  • the middle layer 11g and the middle hard layer 11f correspond to the step B1bh
  • the upper layer 11e corresponds to the uniform region B1a. That is, the lower layer 11i and the lower hard layer 11h have a thickness Ti
  • the middle layer 11g and the middle hard layer 11f have a thickness (Th-Ti)
  • the upper layer 11e has a thickness (Tg-Th).
  • the lower hard layer 11h and the middle hard layer 11f have the smallest etching rate with respect to the other three layers.
  • the lower hard layer 11h and the middle hard layer 11f only have to have a thickness that changes the etching rate as described later, and are desirably as thin as possible.
  • the lower layer 11i has the smallest etching rate among the lower layer 11i, the middle layer 11g, and the upper layer 11e.
  • the middle layer 11g has a higher etching rate than the lower layer 11i.
  • the upper layer 11e has an etching rate smaller than that of the middle layer 11g.
  • the etching rates of the lower layer 11i, the middle layer 11g, and the upper layer 11e are set in proportion to the inclined shape of the side surfaces and the width dimension B1bh and the width dimension B1bi of the step.
  • the resist layer 14 is formed by exposing and developing the photoresist layer 14. Next, the portion of the phase shift layer 11 from which the photoresist layer 14 has been removed as the resist pattern 14a is exposed to an etching solution, whereby 11e, 11f, 11g, 11h, and 11i are simultaneously etched to etch each layer. Due to the rate difference, a shape as shown in FIG. 4C is obtained.
  • the etching rates of the middle hard layer 11f and the lower hard layer 11h are smaller than the etching rates of the upper layer 11e, the middle layer 11g, and the lower layer 11i, these serve as an etching rate changing layer. For this reason, when the layer located below the upper layer 11e is etched, the upper layer 11e located above the middle hard layer 11f is etched from the side, and the uniform region B1a is compared with the middle hard layer 11f.
  • a step B1bh can be formed by being recessed inward.
  • a step B1bi can be formed by being recessed to the side.
  • the resist pattern 14a in FIG. 4D is removed.
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 14a.
  • the upper layer 11e is also etched when the middle layer 11g is etched, and the lower layer 11i
  • the upper layer 11f and the middle layer 11g are also etched to form the stepped portion B1bh and the stepped portion B1bi as shown in FIG.
  • the etching rate is controlled by setting the flow rate ratio of the oxidizing gas when forming the phase shift layer 11, so that the side surface in the multi-stage region B1b is substantially vertical, that is, The side surface can be formed so as not to be inclined.
  • the step portions B1bh and B1bi having thicknesses corresponding to the h line and i line can be positioned in a narrower range, the accuracy of the exposure pattern shape can be further improved.
  • FIG. 5 is a schematic cross-sectional view showing the phase shift mask according to the present embodiment
  • FIG. 6 is a process diagram schematically showing the method for manufacturing the phase shift mask according to the present embodiment. It is a phase shift mask. 5 and FIG. 6, parts corresponding to those in FIGS. 1 to 4 are denoted by the same reference numerals, and description thereof is omitted.
  • the phase shift mask M2 of the present embodiment is provided on the surface of a glass substrate (transparent substrate) S, and a phase shift pattern 11a capable of giving a phase difference of 180 ° is located on the lower side.
  • a so-called underlay type phase shift mask is provided in which the light shielding pattern 13b is positioned above the etching stopper pattern 12b.
  • the phase shift mask M2 has a boundary portion B1 between the exposed portion C of the glass substrate S and the phase shift pattern 11a in plan view in the exposure region where the exposure pattern is formed. And a light shielding region B2 in which a light shielding pattern 13b is formed via an etching stopper pattern 12b on the upper side of the phase shift pattern 11a.
  • the thickness of the phase shift pattern 11a is set to a constant value Tg, and the boundary portion B1 where only the phase shift pattern 11a is formed so as to surround the light shielding region B2 serving as the exposure pattern in plan view. Is located.
  • the uniform thickness region B1a is located on the light shielding region B2 side
  • the multistage region B1b is located on the exposed portion C side of the glass substrate S.
  • the phase shift mask blanks MB of the present invention has a phase shift layer 11 containing Cr as a main component and a main component containing Ni on a glass substrate S using a DC sputtering method. It is manufactured by sequentially forming an etching stopper layer 12 and a light shielding layer 13 mainly composed of Cr. Each of these layers is formed with a uniform thickness in the in-plane direction of the glass substrate S.
  • the film formation conditions at the time of forming the phase shift layer 11 are the film formation conditions in the above-described embodiment, and the film thickness at the time of film formation is set.
  • phase shift mask M2 for manufacturing the phase shift mask M2 from the phase shift mask blanks MB.
  • a photoresist layer 14 is formed on the light shielding layer 13 which is the uppermost layer of the phase shift mask blank MB.
  • the photoresist layer 14 may be a positive type or a negative type.
  • a resist pattern 14 a is formed on the light shielding layer 13 by exposing and developing the photoresist layer 14.
  • the resist pattern 14 a functions as an etching mask for the light shielding layer 13, and the shape is appropriately determined according to the etching pattern of the light shielding layer 13.
  • a shape having an opening width corresponding to the opening width dimension of the phase shift pattern to be formed is set.
  • the light shielding layer 13 is wet etched using the first etching solution over the resist pattern 14a.
  • the first etching solution an etching solution containing cerium diammonium nitrate can be used.
  • cerium diammonium nitrate containing an acid such as nitric acid or perchloric acid is preferably used.
  • the etching stopper layer 12 has high resistance to the first etching solution, only the light shielding layer 13 is patterned to form the light shielding pattern 13a.
  • the light shielding pattern 13a has a shape having an opening width corresponding to the resist pattern 14a.
  • the etching stopper layer 12 is wet etched using the second etching solution over the resist pattern 14a.
  • the second etching solution a solution obtained by adding at least one selected from acetic acid, perchloric acid, aqueous hydrogen peroxide and hydrochloric acid to nitric acid can be suitably used.
  • the etching stopper layer 12 is patterned to form the etching stopper pattern 12a.
  • the etching stopper pattern 12a has a shape having an opening width corresponding to the opening width dimension of the light shielding pattern 13a and the resist pattern 14a.
  • the phase shift layer 11 is wet etched using the first etching solution over the resist pattern 14a, that is, without removing the resist pattern 14a.
  • the phase shift layer 11 is patterned to form the phase shift pattern 11a.
  • a portion C where the glass substrate S is exposed is formed.
  • the phase shift layer 11 formed as a multilayer having different etching rates is etched, and as shown in detail in FIG.
  • the phase shift pattern 11a is formed with the multistage region B1b having B1bi.
  • the light shielding pattern 13a is further side-etched to form a light shielding pattern 13b having a light shielding region B2 having an opening width larger than the opening width dimension of the phase shift pattern 11a.
  • the etching stopper layer 12a exposed from the side surface of the light shielding pattern 13b is wet-etched using a second etching solution to form an resist pattern as an etching stopper pattern 12b having an opening width corresponding to the opening width dimension of the light shielding pattern 13b.
  • the pattern 14a is removed. Since a known resist stripping solution can be used to remove the resist pattern 14a, detailed description is omitted here.
  • the boundary portion B1 including only the phase shift pattern 11a is formed so as to surround the light shielding region B2, and the boundary portion B1 is positioned on the exposed portion C side of the glass substrate S.
  • the multistage region B1b and the uniform thickness region B1a located on the light shielding region B2 side are formed, and the opening width of the light shielding pattern 13b (and the etching stopper pattern 12b) is larger than the opening width of the phase shift pattern 11a.
  • a wide edge-enhanced phase shift mask M2 is obtained.
  • FIG. 6 shows that the side surface of the phase shift pattern 11a is formed vertically, but in reality, a step B1bh and a step B1bi are formed as shown in FIG. Further, in FIG. 6, the side surfaces of the light shielding pattern 13b are shown to be formed vertically, but actually, as shown in FIG. 5, an inclined surface 13s is formed.
  • the phase shift layer 11 when the phase shift layer 11, the etching stopper layer 12, and the light shielding layer 13 are laminated in this order on the transparent substrate S to form the phase shift mask blanks MB, the phase shift layer 11 is formed.
  • the etching rate By controlling the etching rate by setting the flow rate ratio of the oxidizing gas at the time, the edge-enhanced phase shift mask M2 having the multistage region B1b can be manufactured. Therefore, the phase shift mask M with high definition and high visibility can be manufactured.
  • the boundary portion B1 in which only the phase shift pattern 11a is stacked.
  • setting the thickness of the boundary portion B1 including the multistage region B1b by setting the oxidizing gas flow rate ratio at the time of forming the phase shift layer 11 in the same manner as the single-phase phase shift mask M1 described above.
  • the phase shift layer 11 is composed of any one selected from Cr oxide, nitride, carbide, oxynitride, carbonitride, and oxycarbonitride, and exhibits a phase shift effect sufficiently.
  • the line roughness is substantially linear, and optically with respect to light having a composite wavelength, a multistage region B1b (boundary portion) having a stepped portion B1bh and a stepped portion B1bi corresponding to a vertical pattern cross section. B1). Therefore, it is possible to form a favorable pattern as a photomask.
  • the adhesion strength between the light shielding layer 13 containing Cr and the phase shift layer 11 containing Cr can be sufficiently increased.
  • the shape of the multistage region B1b (boundary portion B1) having the stepped portion B1bi can be obtained.
  • the etching rate of the light shielding pattern 13 a is affected by the composition of the light shielding layer 13 and the interface state between the etching stopper layer 12 and the light shielding layer 13.
  • the ratio of the chromium component in the layer mainly composed of chromium can be increased.
  • the etching rate can be increased, the etching rate can be decreased by reducing the ratio of the chromium component.
  • the etching amount of the light shielding pattern 13a can be set, for example, within a range of 200 nm to 1000 nm.
  • the phase shift layer 11 and the phase shift at the interface between the etching stopper layer 12 and the light shielding layer 13 and the etching stopper layer 12 and the phase shift layer 11 are set by setting the flow rate ratio of the oxidizing gas when forming the phase shift layer 11.
  • the etching rate with the layer 11 can be set within a suitable range. Therefore, the CD of the light shielding pattern 13b and the phase shift pattern 11a to be formed is controlled by controlling the etching amount at the interface between the light shielding layer 13 and the etching stopper layer 12 or in the vicinity of the interface between the etching stopper layer 12 and the phase shift layer 11.
  • the accuracy can be improved, and the cross-sectional shape of the film can be a shape having a multistage region B1b that is favorable for a photomask.
  • the phase shift mask M1 has a multi-stage region having a step B1bh and a step B1bi capable of giving a phase difference of 180 ° to any light in the wavelength region of 300 nm to 500 nm. It has the phase shift pattern 11a in which B1b was formed. Therefore, according to the above manufacturing method, it is possible to improve the pattern accuracy based on the phase shift effect by using the light in the above wavelength region, further increase the depth of focus, and form a fine and highly accurate pattern. Is possible. Thereby, a high-quality flat panel display can be manufactured.
  • the patterned light shielding layer (light shielding pattern) 13 is formed by etching a necessary portion.
  • the light shielding layer 13 may be formed after forming a resist pattern in which the formation region of the light shielding layer 13 is opened. After the light shielding layer 13 is formed, the light shielding layer 13 can be formed in a necessary region by removing the resist pattern (lift-off method).
  • phase shift mask of the present invention it is formed on the transparent substrate, the phase shift layer mainly composed of Cr formed on the surface of the transparent substrate, and the surface of the phase shift layer on the side away from 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, and the above-mentioned side on the side away from the phase shift layer
  • the ratio of the width dimension of the side surface in plan view to the thickness dimension of the phase shift layer is set to a predetermined value. Can be set to a range.
  • FIG. 7 is a schematic cross-sectional view showing the phase shift mask according to the present embodiment.
  • FIG. 8 is a process diagram schematically showing the method of manufacturing the phase shift mask according to the present embodiment, in which M3 is a phase shift mask. 7 and 8, parts corresponding to those in FIGS. 1 to 6 are given the same reference numerals, and descriptions thereof are omitted.
  • the phase shift mask M3 of the present embodiment is provided on the surface of the glass substrate (transparent substrate) S, and the phase shift pattern 11a capable of having a phase difference of 180 ° is positioned on the upper side.
  • the phase shift mask M3 has a boundary portion B1 between the exposed portion C of the glass substrate S and the phase shift pattern 11a in plan view in the exposure region where the exposure pattern is formed. And a light shielding region B3 in which a light shielding pattern 13a is formed below the phase shift pattern 11a.
  • the thickness of the phase shift pattern 11a is set to a constant value T11, and the boundary portion B1 including only the phase shift pattern 11a is positioned so as to surround the light-shielding region B3 serving as the exposure pattern in plan view. ing.
  • a uniform region B1a having a thickness Tg is located on the light shielding region B3 side, and a multistage region B1b is located on the exposed portion C side of the glass substrate S.
  • the light shielding layer 13 is formed on the glass substrate S as shown in FIG.
  • a photoresist layer 14 is formed on the light shielding layer 13.
  • the photoresist layer 14 is exposed and developed to remove the region 14 p of the photoresist layer 14, and the resist pattern 14 a is formed on the light shielding layer 13. It is formed.
  • the resist pattern 14 a functions as an etching mask for the light shielding layer 13, and the shape is appropriately determined according to the etching pattern of the light shielding layer 13.
  • the light shielding layer 13 is patterned into a predetermined pattern shape by etching.
  • the light shielding pattern 13a of a predetermined shape is formed on the glass substrate S.
  • a wet etching method or a dry etching method can be applied.
  • the substrate S is large, the wet etching method is adopted from the viewpoint of cost because the substrate is large.
  • the etching solution for the light shielding layer 13 can be appropriately selected.
  • the light shielding layer 13 is made of a chromium-based material, for example, an aqueous solution of ceric ammonium nitrate and perchloric acid can be used.
  • this etching solution has a high selection ratio with the glass substrate, the glass substrate S can be protected during patterning of the light shielding layer 13.
  • the light shielding layer 13 is made of a metal silicide material, for example, ammonium hydrogen fluoride can be used as the etchant.
  • the resist pattern 14a is removed as shown in FIG.
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 14a.
  • the phase shift layer 11 is formed.
  • the phase shift layer 11 is formed so as to cover the light shielding pattern 13a on almost the entire surface of the glass substrate S.
  • a film formation method of the phase shift layer 11 an electron beam (EB) vapor deposition method, a laser vapor deposition method, an atomic layer film formation (ALD) method, an ion assist sputtering method, or the like can be applied, particularly in the case of a large substrate.
  • EB electron beam
  • ALD atomic layer film formation
  • an ion assist sputtering method or the like
  • 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 11 is made of a chromium-based material.
  • the phase shift layer 11 is made of, for example, oxynitride chromium carbide. According to the chromium-based material, good patternability can be obtained particularly on a large substrate.
  • the flow rate ratio in the atmosphere gas of the oxidizing gas is set in the same manner as the film formation conditions in the above-described embodiment, so that the phase shift layer in the etching process is set. 11 is controlled to control the inclined state of the inclined surface 11s.
  • a photoresist layer 14 is formed on the phase shift layer 11 as shown in FIG.
  • a resist pattern 14a is formed on the phase shift layer 11 by exposing and developing the photoresist layer 14.
  • the resist pattern 14 a functions as an etching mask for the phase shift layer 11, and the shape is appropriately determined according to the etching pattern of the phase shift layer 11.
  • the phase shift layer 11 is etched into a predetermined pattern shape.
  • the phase shift pattern 11a having a predetermined shape and the exposed portion C of the glass substrate S are formed on the glass substrate S.
  • the wet etching method is adopted in terms of in-plane uniformity of processing and cost.
  • the etching solution for the phase shift layer 11 can be appropriately selected.
  • ceric ammonium nitrate and an aqueous solution of perchloric acid can be used. Since this etching solution has a high selectivity with respect to the glass substrate, the glass substrate S can be protected when the phase shift layer 11 is patterned.
  • phase shift layer 11 formed as a multilayer having different etching rates is etched, and as shown in detail in FIG.
  • the phase shift pattern 11a is formed with the multistage region B1b having B1bi.
  • phase shift mask M3 is manufactured as shown in FIG.
  • a sodium hydroxide aqueous solution can be used for removing the resist pattern 14a.
  • the phase shift mask M3 in which the light shielding pattern 13a and the phase shift pattern 11a are stacked in this order as the light shielding region B3 is formed with only the phase shift pattern 11a.
  • a high-definition edge-enhanced phase shift mask M3 can be manufactured by positioning the thickness portion corresponding to each wavelength in a predetermined range along the shape of the light-shielding region B3 (pattern contour).
  • the uniform region B1a can be changed as shown in FIG. 1, FIG. 3 to FIG.
  • the side surface shape has two stages of the stepped part B1bh and the stepped part B1bi.
  • this is only a composite wavelength light including three wavelengths of g-line, h-line, and i-line. This is not the case when the wavelength used for exposure is different from these three wavelengths.
  • the thickness settings of these steps will also change in response to the applied wavelength. Further, the thickness of these step portions can be controlled to a desired state because of the necessity of optical phase adjustment.
  • a chromium oxynitride and carbonized film of the phase shift layer 11 was formed on the glass substrate S to a thickness of 145 nm by sputtering.
  • a resist pattern 14a is formed on the phase shift layer 11, and the phase shift layer 11 is etched by using a mixed etching solution of ceric ammonium nitrate and perchloric acid over the resist pattern 14a. By forming this, the following edge-enhanced phase shift mask M1 was obtained.
  • the oxidizing gas flow rate of the atmospheric gas was changed as the film forming condition of the phase shift layer 11, and the value of the width dimension B1b of the multistage region after etching was measured.
  • the result is shown as the relationship between the ratio of the phase shift layer 11 to the thickness T11 and the flow rates of Ar as the inert gas, N 2 as the nitriding gas, and CO 2 as the oxidizing gas.
  • the flow ratio is Carbon dioxide flow rate / (Ar gas flow rate + N 2 gas flow rate + CO 2 gas flow rate) ⁇ 100 Value of What is distance / film thickness? It is a value of (width B1b of the inclined surface 11s in plan view) / (thickness T11 of the phase shift layer 11).
  • Table 1 is an example of a multi-layered state having an effect on exposure of two wavelengths of i-line and h-line as a specific example corresponding to the first embodiment shown in FIG.
  • Tables 2 and 3 are examples of multi-layered states having effects on exposure of three wavelengths of i-line, h-line, and g-line in Tables 2 and 3 as specific examples corresponding to the first embodiment shown in FIG. It is.
  • the thickness of the etching rate changing layer with the etching rate changed may be other than 1.0 nm, not limited to this example, and the etching rate changing layer is formed.
  • the amount of oxidizing gas in is effective under the following conditions. Further, neither the layer having a film thickness corresponding to the exposure wavelength nor the gas condition is limited to the conditions shown in Tables 1 to 3.
  • the optimum range of the gas flow rate is 7.3-25 sccm (that is, 3.68% to 11.60%) under the condition of low CO 2 in which the side surface of the boundary portion B1 including the multistage region B1b is vertical, that is, the cross section is vertical.
  • the range of 25-63.3 sccm (11.60% to 24.89%) is preferable under the condition of CO 2 height where the side surface of the boundary portion B1 including the multi-stage region B1b is vertical, that is, horizontal in cross section. I understand that.

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WO2019003486A1 (ja) * 2017-06-28 2019-01-03 アルバック成膜株式会社 マスクブランクス、位相シフトマスク、ハーフトーンマスク、マスクブランクスの製造方法、及び位相シフトマスクの製造方法
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