WO2017141605A1 - マスクブランク、位相シフトマスクの製造方法、及び半導体デバイスの製造方法 - Google Patents

マスクブランク、位相シフトマスクの製造方法、及び半導体デバイスの製造方法 Download PDF

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WO2017141605A1
WO2017141605A1 PCT/JP2017/001343 JP2017001343W WO2017141605A1 WO 2017141605 A1 WO2017141605 A1 WO 2017141605A1 JP 2017001343 W JP2017001343 W JP 2017001343W WO 2017141605 A1 WO2017141605 A1 WO 2017141605A1
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Prior art keywords
film
shielding film
light
light shielding
mask
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English (en)
French (fr)
Japanese (ja)
Inventor
亮 大久保
野澤　順
博明 宍戸
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Hoya Corp
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Hoya Corp
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Priority to KR1020187021041A priority Critical patent/KR102703442B1/ko
Priority to JP2017567992A priority patent/JP6396611B2/ja
Priority to US16/076,384 priority patent/US20190040516A1/en
Publication of WO2017141605A1 publication Critical patent/WO2017141605A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • 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
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/0605—Carbon
    • 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
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; 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
    • G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; 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
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching

Definitions

  • the present invention relates to a mask blank, a method of manufacturing a phase shift mask using the mask blank, and a method of manufacturing a semiconductor device using a phase shift mask manufactured from the mask blank.
  • a mask blank for a phase shift mask As a mask blank for a phase shift mask, a mask blank having a light-shielding film made of a chromium-based material on a light-transmitting substrate has been known.
  • a phase shift mask formed using such a mask blank includes a light shielding pattern formed by patterning a light shielding film by dry etching using a mixed gas of chlorine-based gas and oxygen gas.
  • Patent Document 1 As a mask blank using a chromium-based material, it has been proposed to use a multilayer film in which CrOC and CrOCN are combined as a light shielding film and an antireflection film (see, for example, Patent Document 1).
  • a mask blank for patterning the light-shielding film by dry etching using a mixed gas of chlorine-based gas and oxygen gas an etching mask of a silicon-based material such as SiO 2 , SiN, or SiON on the light-shielding film of a chromium-based material
  • a configuration having a film has been proposed (see, for example, Patent Document 2).
  • tantalum-based materials such as Ta, TaN, and TaON are listed as materials suitable for the etching mask film in addition to the silicon-based material described above.
  • a mixed gas of chlorine-based gas and oxygen gas oxygen-containing chlorine-based gas
  • oxygen-containing chlorine-based gas oxygen-containing chlorine-based gas
  • dry etching using this oxygen-containing chlorine-based gas as an etching gas has a small tendency for anisotropic etching and a large tendency for isotropic etching.
  • the control of the etching direction by applying a bias voltage is high, and the etching anisotropy is high. Therefore, the side etching amount of the thin film to be etched can be made minute.
  • oxygen gas tends to be radical plasma, so the effect of controlling the etching direction by applying a bias voltage is small, and etching anisotropy is increased. It is difficult. For this reason, when a pattern is formed on a light-shielding film made of a chromium-based material by dry etching using an oxygen-containing chlorine-based gas, the side etching amount tends to increase.
  • the resist pattern is etched from the top and decreases. At this time, the side wall direction of the resist pattern is also etched to be reduced. For this reason, the width of the pattern formed on the resist film is designed in advance in consideration of the amount of decrease due to side etching. Further, the width of the pattern formed on the resist film is designed in consideration of the side etching amount of the light shielding film of the chromium-based material.
  • a mask blank provided with a hard mask film made of a material having sufficient etching selectivity with a chromium-based material for dry etching of an oxygen-containing chlorine-based gas on a light-shielding film of a chromium-based material has been provided. It is starting to be used.
  • a pattern is formed on the hard mask film by dry etching using the resist pattern as a mask.
  • oxygen-containing chlorine-based gas is dry-etched on the light shielding film to form a pattern on the light shielding film.
  • This hard mask film is generally formed of a material that can be patterned by dry etching of a fluorine-based gas.
  • the fluorine-based gas dry etching is ion-based etching, there is a large tendency for anisotropic etching. For this reason, the side etching amount of the pattern side wall in the hard mask film on which the transfer pattern is formed is small. In the case of fluorine gas dry etching, the amount of side etching tends to be small even in a resist pattern for forming a pattern on a hard mask film. For this reason, the demand for a small amount of side etching in dry etching of an oxygen-containing chlorine-based gas is also increasing for a light-shielding film of a chromium-based material.
  • the bias voltage applied during the dry etching is significantly increased (hereinafter, an oxygen-containing chlorine-based gas with an increased ratio of the chlorine-based gas is used, and Dry etching performed under the condition of applying a high bias voltage is also referred to as “high bias etching of oxygen-containing chlorine-based gas”).
  • the mask blank described in the above-mentioned Patent Document 1 has a configuration in which films of chromium-based materials having different compositions are stacked, and the etching rate differs depending on the composition of each film.
  • the side etching amount is also different.
  • the mask blank was used to pattern the light shielding film by dry etching using high bias etching, a large step was generated in the cross-sectional shape of the pattern side wall formed in the light shielding film. If a phase shift mask is created using a mask blank having a step in the cross-sectional shape of the side wall, the pattern accuracy of the light shielding film is lowered.
  • a light-shielding film formed of a material containing chromium and a hard mask film formed in contact with the light-shielding film are laminated in this order on a light-transmitting substrate.
  • a mask blank in which the amount of side etching is significantly reduced while maintaining good pattern accuracy.
  • this invention provides the manufacturing method of the phase shift mask which can form a fine pattern accurately in a light shielding film by using this mask blank. Furthermore, a method for manufacturing a semiconductor device using the phase shift mask is provided.
  • the present invention has the following configuration as means for solving the above problems.
  • the hard mask film is made of a material containing one or more elements selected from silicon and tantalum,
  • the light shielding film has an optical density of more than 2.0 with respect to exposure light of an ArF excimer laser,
  • the light-shielding film is a single-layer film having a composition gradient portion with an increased oxygen content in the surface on the hard mask film side and in the vicinity thereof,
  • the light shielding film is made of a material containing chromium, oxygen and carbon,
  • the portion excluding the composition gradient portion of the light shielding film has a chromium content of 50 atomic% or more,
  • the maximum peak of the N1s narrow spectrum obtained by analyzing by X-ray photoelectron spectroscopy is below the detection lower limit
  • a portion of the light shielding film excluding the composition gradient portion has a maximum peak in a narrow spectrum of Cr2p
  • composition gradient portion of the light-shielding film has a maximum peak of a Cr2p narrow spectrum obtained by analysis by X-ray photoelectron spectroscopy at a binding energy of 576 eV or more.
  • (Configuration 4) 4. The mask blank according to any one of configurations 1 to 3, wherein the light shielding film has a maximum peak of a narrow spectrum of Si2p obtained by analysis by X-ray photoelectron spectroscopy that is equal to or lower than a detection lower limit value.
  • (Configuration 10) A method of manufacturing a phase shift mask using the mask blank according to any one of configurations 1 to 9, Forming a light shielding pattern on the hard mask film by dry etching using a fluorine-based gas using a resist film having a light shielding pattern formed on the hard mask film as a mask; Forming a light-shielding pattern on the light-shielding film by dry etching using a mixed gas of chlorine-based gas and oxygen gas using the hard mask film on which the light-shielding pattern is formed as a mask; Using a resist film having an digging pattern formed on the light shielding film as a mask, and forming a digging pattern on the translucent substrate by dry etching using a fluorine-based gas. A method of manufacturing a phase shift mask.
  • (Configuration 11) A method of manufacturing a semiconductor device, comprising using the phase shift mask according to Structure 10 and exposing and transferring a transfer pattern onto a resist film on a semiconductor substrate.
  • a mask blank having the above configuration having a structure in which a light-shielding film formed of a material containing chromium and a hard mask film are laminated in this order on a light-transmitting substrate.
  • oxygen-containing chlorine gas is used as an etching gas and this light shielding film is patterned by dry etching under high bias etching conditions, the amount of side etching of the pattern of the light shielding film formed thereby is greatly reduced. And a fine pattern can be formed on the light shielding film with high accuracy. For this reason, a phase shift mask provided with a highly accurate and fine transfer pattern can be obtained. Furthermore, in manufacturing a semiconductor device using this phase shift mask, it becomes possible to transfer a pattern with good accuracy to a resist film or the like on the semiconductor device.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a mask blank. It is a sectional schematic diagram showing a manufacturing process of a phase shift mask. It is a sectional schematic diagram showing a manufacturing process of a phase shift mask. It is a figure which shows the result (Cr2p narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 1. FIG. It is a figure which shows the result (O1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 1.
  • FIG. 1 It is a figure which shows the result (N1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 1.
  • FIG. It is a figure which shows the result (C1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 1.
  • FIG. It is a figure which shows the result (Si2p narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 1.
  • FIG. 1 It is a figure which shows the result (C1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 2.
  • FIG. It is a figure which shows the result (Si2p narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on Example 2.
  • FIG. It is a figure which shows the result (Cr2p narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on the comparative example 1.
  • FIG. 1 It is a figure which shows the result (O1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on the comparative example 1.
  • FIG. It is a figure which shows the result (N1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on the comparative example 1.
  • FIG. It is a figure which shows the result (C1s narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on the comparative example 1.
  • FIG. It is a figure which shows the result (Si2p narrow spectrum) which performed the XPS analysis (depth direction chemical bond state analysis) with respect to the light shielding film of the mask blank which concerns on the comparative example 1.
  • a chromium (Cr) -based material constituting a conventional mask blank a material containing nitrogen (N) such as CrON or CrOCN is known. This is because the defect quality of the chromium-based material film is improved by using nitrogen gas as the reactive gas in addition to the gas containing oxygen when the chromium-based material is formed by sputtering. In addition, by adding nitrogen to the chromium-based material film, the etching rate for dry etching with an oxygen-containing chlorine-based gas is increased.
  • a film forming method in which pre-sputtering is performed at the time of film formation of a Cr-based material has been performed on a chromium-based material film.
  • pre-sputtering it is possible to improve the defect quality of the chromium-based material film, and therefore it is possible to form a film without using N 2 gas for improving the defect quality.
  • the dry etching in the high bias etching for the chromium-based material film is compared with the dry etching performed in the normal bias voltage using the same etching gas condition (hereinafter referred to as “dry etching under normal conditions”).
  • dry etching under normal conditions the same etching gas condition
  • the etching rate of etching in the film thickness direction can be greatly increased.
  • both chemical etching and physical action etching are performed.
  • Etching by a chemical reaction is performed by a process in which an etching gas in a plasma state comes into contact with the surface of the thin film and combines with a metal element in the thin film to generate a low boiling point compound and sublimate.
  • etching by chemical reaction a metal element in a bonded state with another element is broken to form a low-boiling compound.
  • ionic plasma in an etching gas accelerated by a bias voltage collides with the surface of the thin film (this phenomenon is also referred to as “ion bombardment”).
  • ion bombardment a phenomenon of generating and sublimating the metal element and a low boiling point compound is performed.
  • High bias etching is an improvement of dry etching due to physical action compared to dry etching under normal conditions.
  • Etching by physical action greatly contributes to etching in the film thickness direction, but does not contribute much to etching in the side wall direction of the pattern.
  • etching by chemical reaction contributes to both etching in the film thickness direction and etching in the side wall direction of the pattern. Therefore, in order to make the side etching amount smaller than before, the ease of etching by a chemical reaction in a light shielding film of a chromium-based material is reduced compared to the past, and the ease of dry etching by a physical action is reduced compared with the past. It is necessary to maintain the same level.
  • the simplest approach for reducing the etching amount related to the etching by chemical reaction in the light shielding film of the chromium-based material is to increase the chromium content in the light shielding film.
  • the etching amount related to the dry etching due to the physical action is significantly reduced.
  • Even in the case of dry etching by physical action if the chromium element repelled from the film does not combine with chlorine and oxygen to form chromyl chloride (CrO 2 Cl 2 , a low boiling point compound of chromium), The element is reattached to the light shielding film and is not removed. Since there is a limit to increasing the supply amount of the etching gas, if the chromium content in the light shielding film is too large, the etching rate of the light shielding film is significantly reduced.
  • the etching time for patterning the light shielding film is significantly increased. If the etching time for patterning the light shielding film becomes longer, the time for which the side wall of the light shielding film is exposed to the etching gas becomes longer, leading to an increase in the amount of side etching.
  • An approach that greatly reduces the etching rate of the light shielding film, such as increasing the chromium content in the light shielding film, does not lead to suppression of the side etching amount.
  • constituent elements other than chromium in the light shielding film In order to suppress the side etching amount, it is effective to contain a light element that consumes oxygen radicals that promote etching by a chemical reaction. Since the material for forming the light-shielding film is required to have at least a certain level of patterning characteristics, light-shielding performance, chemical resistance during cleaning, etc., light elements that can be contained in a certain amount or more in the chromium-based material forming the light-shielding film are Limited. Typical examples of light elements to be contained in a chromium-based material in a certain amount or more include oxygen, nitrogen, and carbon.
  • the etching rate is significantly increased in both high bias etching and dry etching under normal conditions.
  • the etching of the side etching easily proceeds, but the etching time in the film thickness direction is greatly shortened, and the time during which the side wall of the light shielding film is exposed to the etching gas is shortened.
  • the chromium-based material for forming the light shielding film needs to contain oxygen.
  • the etching rate is high in both cases of high bias etching and dry etching under normal conditions, although not as remarkable as when oxygen is contained.
  • side etching also proceeds easily. Considering the fact that the etching time in the film thickness direction is shortened by adding nitrogen to the chromium-based material forming the light-shielding film, considering that the ease of side etching proceeds, in the case of high bias etching, It can be said that the chromium-based material forming the light-shielding film should not contain nitrogen.
  • the etching rate is slightly slower than in the case of the light-shielding film made only of chromium.
  • the resistance to etching by a physical action becomes lower than in the case of a light-shielding film made only of chromium.
  • the etching rate becomes faster than that in the case of the light shielding film made only of chromium.
  • the chromium-based material forming the light shielding film when carbon is contained in the chromium-based material forming the light shielding film, oxygen radicals that promote side etching are consumed, so that side etching is less likely to proceed than when oxygen or nitrogen is contained. Considering these, in the case of high bias etching, the chromium-based material for forming the light shielding film needs to contain carbon.
  • the Cr—N bond has a low binding energy (binding energy) and tends to be easily dissociated. For this reason, when chlorine and oxygen in a plasma state come into contact with each other, the Cr—N bond is dissociated and a low boiling point chromyl chloride is easily formed.
  • the Cr—C bond has a high binding energy and tends to be difficult to dissociate. For this reason, even if chlorine and oxygen in the plasma state come into contact with each other, it is difficult to dissociate the Cr—C bond and form low boiling point chromyl chloride.
  • the light-shielding film that is dry-etched by high bias etching using the hard mask film on which the pattern is formed as an etching mask contains oxygen on the surface on the hard mask film side and in the vicinity thereof.
  • the light-shielding film is made of a material containing chromium, oxygen, and carbon, and the portion other than the composition-gradient part of the light-shielding film has a chromium content of 50 atoms.
  • the maximum peak of the N1s narrow spectrum obtained by analyzing by X-ray photoelectron spectroscopy (XPS) is below the detection lower limit value, and the light shielding film has a composition gradient of the light shielding film.
  • the part excluding the part has a maximum peak at a binding energy of 574 eV or less in the narrow spectrum of Cr2p obtained by analysis by X-ray photoelectron spectroscopy. I came to the conclusion that there should be.
  • FIG. 1 shows a schematic configuration of an embodiment of a mask blank.
  • a mask blank 100 shown in FIG. 1 has a configuration in which a light shielding film 3 and a hard mask film 4 are laminated in this order on one main surface of a translucent substrate 1.
  • the mask blank 100 may have a configuration in which a resist film is laminated on the hard mask film 4 as necessary.
  • details of main components of the mask blank 100 will be described.
  • the translucent substrate 1 is made of a material having good transparency with respect to the exposure light used in the exposure process.
  • synthetic quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (such as SiO 2 —TiO 2 glass), and other various glass substrates can be used.
  • a substrate using synthetic quartz glass has high transmittance with respect to ArF excimer laser light (wavelength: about 193 nm), it can be suitably used as the light-transmitting substrate 1 of the mask blank 100.
  • the exposure process here refers to a transfer mask (phase shift mask) manufactured using the mask blank 100 set on a mask stage of an exposure apparatus, and irradiated with exposure light to the transfer object. It is a step of performing exposure transfer of a transfer pattern (phase shift pattern).
  • the exposure light means exposure light used in this exposure process.
  • ArF excimer laser light wavelength: 193 nm
  • KrF excimer laser light wavelength: 248 nm
  • i-line light wavelength: 365 nm
  • the light-shielding film 3 is a film on which a light-shielding pattern is formed when a transfer mask is manufactured from the mask blank 100, and is a film having a light-shielding property with respect to exposure light.
  • the light-shielding film 3 is required to have an optical density (OD) greater than 2.0 with respect to, for example, ArF excimer laser light having a wavelength of 193 nm, preferably 2.8 or more, and more preferably 3.0 or more. .
  • the light-shielding film 3 has a front side (surface farthest from the translucent substrate 1) and a back side (surface on the translucent substrate 1 side) in order to prevent exposure transfer defects due to reflection of exposure light.
  • the surface reflectivity with respect to the exposure light on each surface is kept low.
  • the reflectance of the surface on the front side of the light-shielding film 3 where the reflected light of the exposure light from the reduction optical system of the exposure apparatus hits is desirably, for example, 40% or less (preferably 30% or less). This is to suppress stray light generated by multiple reflection between the front surface of the light shielding film 3 and the lens of the reduction optical system.
  • the light shielding film 3 needs to function as an etching mask at the time of dry etching with a fluorine-based gas for forming a digging pattern on the translucent substrate 1. For this reason, it is necessary to apply a material having sufficient etching selectivity to the light-transmitting substrate 1 in the dry etching using a fluorine-based gas for the light-shielding film 3.
  • the light shielding film 3 is required to be able to form a fine light shielding pattern with high accuracy.
  • the thickness of the light shielding film 3 is preferably 80 nm or less, and more preferably 75 nm or less. If the thickness of the light shielding film 3 is too thick, a fine pattern to be formed cannot be formed with high accuracy.
  • the light shielding film 3 is required to satisfy the required optical density as described above. For this reason, it is calculated
  • the light shielding film 3 is made of a material containing chromium (Cr), oxygen (O), and carbon (C).
  • the light-shielding film 3 is a single-layer film having a composition gradient portion in which the oxygen content increases on the surface on the hard mask film 4 side and in the vicinity thereof. This is because, during the manufacturing process, the surface of the formed light shielding film 3 is exposed to an atmosphere containing oxygen, and therefore, a region in which the oxygen content is increased more than other portions is formed only on the surface of the light shielding film 3.
  • the oxygen content is highest on the surface exposed to the atmosphere containing oxygen, and the oxygen content gradually decreases as the distance from the surface increases. Then, the composition of the light shielding film 3 becomes substantially constant from a position away from the surface to some extent.
  • a region where the oxygen content changes (slowly decreases) from the surface of the light shielding film 3 is defined as a composition gradient portion.
  • the difference in the film thickness direction of the content of each constituent element is preferably less than 10 atomic%, and more preferably 8 atomic% or less. Preferably, it is more preferably 5 atomic% or less.
  • the composition gradient portion of the light shielding film 3 is preferably a region from the surface to a depth of less than 5 nm, more preferably a region to a depth of 4 nm or less, and further a region to a depth of 3 nm or less. preferable.
  • the portion other than the composition gradient portion of the light shielding film 3 has a chromium content of 50 atomic% or more. This is to suppress side etching that occurs when the light shielding film 3 is patterned by high bias etching.
  • the portion of the light shielding film 3 excluding the composition gradient portion preferably has a chromium content of 80 atomic% or less. This is for securing a sufficient etching rate when the light shielding film 3 is patterned by high bias etching.
  • the maximum peak of the N1s narrow spectrum obtained by analysis by X-ray photoelectron spectroscopy is below the detection lower limit.
  • Cr—N bonds exist in the material forming the light-shielding film 3 in a predetermined ratio or more. If the material for forming the light shielding film 3 contains Cr—N bonds in a predetermined ratio or more, it is difficult to suppress the progress of side etching when the light shielding film 3 is patterned by high bias etching.
  • the content of nitrogen (N) in the light-shielding film 3 is preferably not more than a detection limit value in composition analysis by X-ray photoelectron spectroscopy.
  • the portion excluding the composition gradient portion of the light-shielding film 3 has a maximum peak at a binding energy of 574 eV or less in the narrow spectrum of Cr2p obtained by analysis by X-ray photoelectron spectroscopy.
  • a material containing Cr when the narrow spectrum of Cr2p has a maximum peak with a binding energy higher than 574 eV, that is, in a state of chemical shift, it binds to other atoms (particularly nitrogen). It shows that the existing ratio of chromium atoms is high.
  • Such a chromium-based material tends to have low resistance to etching mainly of chemical reaction, and it is difficult to suppress side etching.
  • Suppressing the progress of side etching when patterning by high bias etching is formed by forming a portion of the light shielding film 3 except for the composition gradient portion with a chromium-based material having a maximum peak at a binding energy of 574 eV or less with a narrow spectrum of Cr2p. can do.
  • the narrow spectrum of Cr2p in the part except the composition inclination part of the light shielding film 3 has a maximum peak with the binding energy of 570 eV or less.
  • the ratio obtained by dividing the carbon content [atomic%] in the portion excluding the composition gradient portion of the light shielding film 3 by the total content [atomic%] of chromium, carbon and oxygen is preferably 0.1 or more, More preferably, it is 0.14 or more.
  • the light shielding film 3 occupies most of chromium, oxygen and carbon. Most of the chromium in the light shielding film 3 exists in any form of a Cr—O bond, a Cr—C bond, and a form not bonded to oxygen and carbon.
  • a Cr-based material having a high ratio obtained by dividing the carbon content [atomic%] by the total content of chromium, carbon, and oxygen [atomic%] has a high abundance ratio of Cr—C bonds in the material.
  • the ratio of the carbon content [atomic%] in the portion excluding the composition gradient portion of the light shielding film 3 divided by the total content of chromium and carbon [atomic%] is preferably 0.14 or more, More preferably, it is 0.16 or more.
  • the light shielding film 3 preferably has a total content of chromium, oxygen, and carbon of 95 atomic% or more, and more preferably 98 atomic% or more.
  • the light-shielding film 3 is particularly preferably composed of chromium, oxygen, and carbon except for impurities that are unavoidably mixed. Note that the impurities inevitably mixed here are the light shielding films 3 such as argon (Ar), helium (He), neon (Ne), krypton (Kr), xenon (Xe), hydrogen (H), and the like. An element that is difficult to avoid when forming a film by sputtering.
  • the portion other than the composition gradient portion of the light shielding film 3 preferably has an oxygen content of 10 atomic% to 35 atomic%. Moreover, it is preferable that carbon content is 10 atomic% or more and 20 atomic% or less in the portion excluding the composition gradient portion of the light shielding film 3.
  • the composition gradient portion of the light-shielding film 3 preferably has a maximum peak at a binding energy of 576 eV or more in the narrow spectrum of Cr2p obtained by analysis by X-ray photoelectron spectroscopy.
  • the narrow spectrum of Cr2p of the composition inclination part of the light shielding film 3 has a maximum peak with the binding energy of 580 eV or less.
  • the maximum peak of the narrow spectrum of Si2p obtained by analyzing the light shielding film 3 by X-ray photoelectron spectroscopy is not more than the detection lower limit value.
  • the light shielding film 3 preferably has a silicon content of 1 atomic% or less, and preferably has a detection limit value or less in composition analysis by X-ray photoelectron spectroscopy.
  • a method for obtaining Cr2p narrow spectrum, O1s narrow spectrum, C1s narrow spectrum, N1s narrow spectrum, and Si2p narrow spectrum by performing X-ray photoelectron spectroscopic analysis on the light shielding film 3 is generally performed in the following procedure. . That is, first, a wide spectrum is obtained by performing a wide scan to obtain photoelectron intensity (number of photoelectrons emitted per unit time from a measurement object irradiated with X-rays) with a wide band of binding energy, and the light is blocked. All peaks derived from the constituent elements of the film 3 are specified.
  • each narrow spectrum is performed by performing narrow scan with higher resolution than wide scan but narrow band width of obtainable binding energy around the peak of interest (Cr2p, O1s, C1s, N1s, Si2p, etc.).
  • the step of obtaining the wide spectrum is omitted, and the Cr2p narrow spectrum, the O1s narrow spectrum, the C1s narrow spectrum, the N1s narrow spectrum, and the Si2p narrow spectrum are obtained. Also good.
  • the Cr2p narrow spectrum in the light-shielding film 3 is acquired in the range of the binding energy of, for example, 666 eV to 600 eV. It is more preferable that the Cr2p narrow spectrum in the light shielding film 3 includes a binding energy range of 570 eV to 580 eV.
  • the O1s narrow spectrum in the light shielding film 3 is acquired in the range of the binding energy of 524 eV to 540 eV, for example. It is more preferable that the O1s narrow spectrum in the light shielding film 3 includes a binding energy range of 528 eV to 534 eV.
  • the N1s narrow spectrum in the light shielding film 3 is acquired in the range of the binding energy of 390 eV to 404 eV, for example. It is more preferable that the N1s narrow spectrum in the light shielding film 3 includes a binding energy range of 395 eV to 400 eV.
  • the C1s narrow spectrum in the light shielding film 3 is acquired, for example, in the range of the binding energy of 278 eV to 296 eV. It is more preferable that the C1s narrow spectrum in the light shielding film 3 includes a binding energy range of 280 eV to 285 eV.
  • the Si2p narrow spectrum in the light shielding film 3 is acquired in the range of, for example, a binding energy of 95 eV to 110 eV.
  • the light shielding film 3 can be formed by forming a film on the light-transmitting substrate 1 by a reactive sputtering method using a target containing chromium.
  • the sputtering method may be a method using a direct current (DC) power source (DC sputtering) or a method using a high frequency (RF) power source (RF sputtering).
  • DC sputtering is preferred because the mechanism is simple.
  • the film forming apparatus may be an inline type or a single wafer type.
  • Sputtering gas used when forming the light shielding film 3 includes a gas containing no oxygen (eg, CH 4 , C 2 H 4 , C 2 H 6 ) and a gas containing no oxygen (O). 2 , O 3, etc.) and a rare gas (Ar, Kr, Xe, He, Ne, etc.), a mixed gas containing carbon and oxygen (CO 2 , CO, etc.) and a rare gas, or A mixed gas containing at least one of a gas containing no carbon and containing carbon (CH 4 , C 2 H 4 , C 2 H 6, etc.) and a gas containing no oxygen and containing oxygen in addition to a rare gas and a gas containing carbon and oxygen Is preferred.
  • a gas containing no oxygen eg, CH 4 , C 2 H 4 , C 2 H 6
  • a gas containing no oxygen O. 2 , O 3, etc.
  • a rare gas Ar, Kr, Xe, He, Ne, etc.
  • CO 2 , CO
  • CO 2 gas is less reactive than oxygen gas, the gas can circulate uniformly over a wide area in the chamber. This is preferable because the film quality of the light-shielding film 3 to be formed becomes uniform.
  • introduction method they may be introduced separately into the chamber, or some gases may be introduced together or all gases may be mixed.
  • the material of the target is not limited to chromium alone but may be chromium as a main component, and may be chromium containing either oxygen or carbon, or a target obtained by adding oxygen and carbon to chromium.
  • the hard mask film 4 is provided in contact with the surface of the light shielding film 3.
  • the hard mask film 4 is a film formed of a material having etching resistance against an etching gas used when the light shielding film 3 is etched. It is sufficient for the hard mask film 4 to have a film thickness that can function as an etching mask until dry etching for forming a pattern on the light shielding film 3 is completed. Not subject to restrictions. For this reason, the thickness of the hard mask film 4 can be made much thinner than the thickness of the light shielding film 3.
  • the thickness of the hard mask film 4 is required to be 20 nm or less, preferably 15 nm or less, and more preferably 10 nm or less. This is because if the thickness of the hard mask film 4 is too thick, the thickness of the resist film serving as an etching mask is required in dry etching for forming a light shielding pattern on the hard mask film 4.
  • the thickness of the hard mask film 4 is required to be 3 nm or more, and preferably 5 nm or more. If the thickness of the hard mask film 4 is too thin, the pattern of the hard mask film 4 disappears before the dry etching for forming the light shielding pattern on the light shielding film 3 is completed depending on the conditions of the high bias etching with the oxygen-containing chlorine-based gas. Because there is a risk of doing.
  • a resist film made of an organic material used as an etching mask in dry etching with a fluorine-based gas that forms a pattern on the hard mask film 4 only functions as an etching mask until the dry etching of the hard mask film 4 is completed.
  • the thickness of the film is sufficient. Therefore, the thickness of the resist film can be greatly reduced by providing the hard mask film 4 as compared with the conventional configuration in which the hard mask film 4 is not provided.
  • the hard mask film 4 is preferably formed of a material containing one or more elements selected from silicon and tantalum.
  • the hard mask film 4 is formed of a material containing silicon, it is preferable to apply SiO 2 , SiN, SiON or the like. Further, since the hard mask film 4 in this case tends to have low adhesion to the organic material resist film, the surface of the hard mask film 4 is subjected to HMDS (Hexamethyldisilazane) treatment to improve the surface adhesion. It is preferable.
  • HMDS Hexamethyldisilazane
  • the hard mask film 4 is formed of a material containing tantalum, it is preferable to apply a material in which tantalum contains one or more elements selected from nitrogen, oxygen, boron and carbon in addition to tantalum metal. Examples thereof include Ta, TaN, TaO, TaON, TaBN, TaBO, TaBON, TaCN, TaCO, TaCON, TaBCN, and TaBOCN.
  • the hard mask film 4 is preferably formed of a material containing tantalum (Ta) and oxygen (O) and having an O content of 50 atomic% or more (hereinafter referred to as a TaO-based material).
  • the hard mask film 4 is required to have sufficiently high etching resistance against high bias etching when the light shielding film 3 is patterned. If the etching resistance is not sufficient, the edge portion of the pattern of the hard mask film 4 is etched and the mask pattern is reduced, so that the accuracy of the light shielding pattern is deteriorated.
  • the material containing Ta can greatly increase the resistance to dry etching by the oxygen-containing chlorine-based gas by setting the oxygen content in the material to at least 50 atomic% or more.
  • the TaO-based material hard mask film 4 is desired to have a crystal structure of microcrystal, preferably amorphous.
  • the crystal structure in the TaO-based material hard mask film 4 is microcrystalline or amorphous, it is difficult to form a single structure, and a plurality of crystal structures tend to be mixed.
  • the TaO-based material in the hard mask film 4 tends to be in a state (mixed crystal state) in which TaO bonds, Ta 2 O 3 bonds, TaO 2 bonds, and Ta 2 O 5 bonds are mixed.
  • the TaO-based material in the hard mask film 4 tends to improve the resistance to dry etching with an oxygen-containing chlorine-based gas as the abundance ratio of Ta 2 O 5 bonds increases.
  • the TaO-based material in the hard mask film 4 tends to have higher properties for preventing hydrogen intrusion, chemical resistance, warm water resistance and ArF light resistance as the ratio of Ta 2 O 5 bonds increases.
  • the bonding state of tantalum and oxygen in the film tends to be mainly Ta 2 O 3 bonds.
  • the most unstable TaO bond is considered to be much less than when the oxygen content in the film is less than 50 atomic%.
  • the TaO-based material hard mask film 4 has an oxygen content in the film of 66.7 atomic% or more, it is considered that the bonding state of tantalum and oxygen tends to be mainly TaO 2 bonds. Both the unstable bond TaO bond and the next unstable bond Ta 2 O 3 are considered to be very few.
  • the TaO-based material hard mask film 4 has an oxygen content in the film of 67 atomic% or more, not only TaO 2 bonds are mainly formed but also the ratio of Ta 2 O 5 bonding states becomes high. Conceivable. At such an oxygen content, the Ta 2 O 3 and TaO 2 bonding states rarely exist, and the TaO bonding state cannot exist.
  • the hard mask film 4 made of TaO-based material is considered to be formed substantially only in the bonded state of Ta 2 O 5 when the oxygen content in the film is about 71.4 atomic% (most oxidized) (Because the oxygen content of Ta 2 O 5 in the bonded state is 71.4 atomic%).
  • the TaO-based material hard mask film 4 includes not only Ta 2 O 5 in the most stable bonding state but also bonding states of Ta 2 O 3 and TaO 2. Will be.
  • the lower limit value of the oxygen content that does not affect the dry etching resistance and the amount of the most unstable TaO bond is at least 50 atomic%. It is believed that there is.
  • the Ta 2 O 5 bond is a bonded state having very high stability, and the resistance to high bias etching is greatly increased by increasing the ratio of the Ta 2 O 5 bond. In addition, the characteristics of blocking hydrogen intrusion, chemical resistance, resistance to mask cleaning such as hot water resistance, and ArF light resistance are greatly enhanced.
  • the TaO constituting the hard mask film 4 is formed only by the combined state of Ta 2 O 5 .
  • the hard mask film 4 made of TaO-based material preferably contains nitrogen and other elements in a range that does not affect these functions and effects and does not substantially contain them.
  • the TaO-based material hard mask film 4 is made of a material in which the maximum peak of the Ta4f narrow spectrum obtained by analysis by X-ray photoelectron spectroscopy is larger than 23 eV, thereby greatly improving the resistance to high bias etching. be able to.
  • a material having a high binding energy tends to improve resistance to dry etching by an oxygen-containing chlorine-based gas.
  • the bonding state having the highest bonding energy in the tantalum compound is a Ta 2 O 5 bond.
  • the maximum peak of the Ta4f narrow spectrum obtained by analysis by X-ray photoelectron spectroscopy is preferably 24 eV or more, more preferably 25 eV or more, and 25.4 eV or more. Is particularly preferred. If the maximum peak of the Ta4f narrow spectrum obtained by analysis by X-ray photoelectron spectroscopy is 25 eV or more, the bonding state between tantalum and oxygen in the hard mask film 4 is mainly Ta 2 O 5 bonds, and a high bias Resistance to etching is greatly increased.
  • the TaO-based material having an oxygen content of 50 atomic% constituting the hard mask film 4 has a tendency of tensile stress.
  • the material (CrOC-based material) mainly composed of chromium, oxygen, and carbon constituting the light shielding film 3 has a tendency of compressive stress.
  • a TaO-based material hard mask film 4 is laminated on a CrOC-based material light-shielding film 3, so that the compressive stress of the light-shielding film 3 and the hard mask film 4 There is an offset between the tensile stress and the overall stress of the laminated structure can be reduced.
  • a resist film of an organic material is formed with a thickness of 100 nm or less in contact with the surface of the hard mask film 4.
  • the light shielding pattern to be formed on the light shielding film 3 may be provided with SRAF (Sub-Resolution Assist Feature) having a line width of 40 nm.
  • SRAF Sub-Resolution Assist Feature
  • the film thickness of the resist film can be suppressed by providing the hard mask film 4 as described above, whereby the cross-sectional aspect ratio of the resist pattern formed by this resist film is 1: 2.5. And can be lowered.
  • the resist film preferably has a film thickness of 80 nm or less.
  • the resist film is preferably a resist for electron beam drawing exposure, and more preferably, the resist is a chemical amplification type.
  • the mask blank 100 having the above configuration is manufactured by the following procedure.
  • the translucent substrate 1 has its end face and main surface polished to a predetermined surface roughness (for example, a root mean square roughness Rq of 0.2 nm or less in a square inner region having a side of 1 ⁇ m), and then a predetermined surface roughness.
  • the washing process and the drying process are performed.
  • the light shielding film 3 is formed on the translucent substrate 1 by a sputtering method.
  • the hard mask film 4 is formed on the light shielding film 3 by sputtering.
  • a sputtering target and a sputtering gas containing the material constituting each layer in a predetermined composition ratio are used, and if necessary, a mixed gas of the above rare gas and reactive gas is sputtered. Film formation using gas is performed.
  • the mask blank 100 has a resist film
  • the surface of the hard mask film 4 is subjected to HMDS (Hexamethyldisilazane) treatment as necessary.
  • a resist film is formed on the surface of the hard mask film 4 subjected to the HMDS process by a coating method such as a spin coating method, and the mask blank 100 is completed.
  • a resist film is formed on the hard mask film 4 of the mask blank 100 by a spin coating method.
  • a first pattern to be a light shielding pattern to be formed on the light shielding film 3 is exposed and drawn on the resist film with an electron beam.
  • the central portion of the translucent substrate 1 is used as a transfer pattern forming region 11A, and a light shielding pattern which is one of the transfer patterns is exposed and drawn.
  • an alignment pattern or a bar code pattern is exposed and drawn on the outer peripheral area 11B of the transfer pattern forming area 11A.
  • predetermined processing such as PEB processing, development processing, and post-baking processing is performed on the resist film to form a first pattern (resist pattern 5a) serving as a light shielding pattern on the resist film (see FIG. 2A). ).
  • the transfer pattern includes a light shielding pattern and an engraved pattern (phase shift pattern). Further, an electron beam is often used for exposure drawing of the resist film.
  • the hard mask film 4 is dry-etched using a fluorine-based gas to form a first pattern (hard mask pattern 4a) on the hard mask film 4 (FIG. 2B). reference). Thereafter, the resist pattern 5a is removed.
  • the light shielding film 3 may be dry-etched with the resist pattern 5a remaining without being removed. In this case, the resist pattern 5a disappears when the light shielding film 3 is dry-etched.
  • etching using an oxygen-containing chlorine-based gas is performed to form a first pattern (light shielding pattern 3a) on the light shielding film 3 (see FIG. 2C).
  • Dry etching with oxygen-containing chlorine-based gas on the light-shielding film 3 uses an etching gas having a higher mixing ratio of chlorine-based gas than conventional.
  • the anisotropy of dry etching can be increased.
  • the bias voltage applied from the back side of the translucent substrate 1 is also made higher than before.
  • the power when this bias voltage is applied is preferably 15 [W] or more, more preferably 20 [W] or more, and 30 [W] or more is more preferable.
  • a resist film (second resist film) 6 having a digging pattern is formed on the hard mask film 4 (hard mask pattern 4a) on which the light shielding pattern is formed.
  • a resist film 6 is formed on the translucent substrate 1 by a spin coating method.
  • predetermined processing such as development processing is performed.
  • a digging pattern in which the translucent substrate 1 is exposed is formed in the resist film 6 in the transfer pattern forming region 11A.
  • the digging pattern is formed in the resist film 6 with an opening width that takes a margin of misalignment generated in the exposure process, and the opening of the digging pattern formed in the resist film 6 completely covers the opening of the light shielding pattern.
  • a digging pattern is formed so as to be exposed.
  • the transparent substrate 1 is dried using a fluorine-based gas with the resist film 6 having the digging pattern and the light shielding film 3 on which the light shielding pattern 3a is formed as a mask. Etching is performed. Thereby, the digging pattern 2 is formed on the main surface 11S in the transfer pattern forming region 11A of the translucent substrate 1.
  • the digging pattern 2 has a predetermined phase difference (for example, 150 ° to 190 °) with respect to the exposure light that passes through the transmissive substrate 1 whose surface is not dug. Depth. For example, when ArF excimer laser light is applied to exposure light, the digging pattern is formed with a depth of about 173 nm (when the phase difference is 180 degrees).
  • the resist film 6 is reduced, and the resist film 6 on the hard mask film 4 is completely lost. Further, the hard mask film 4 also disappears by dry etching with a fluorine-based gas. Thereby, the transfer pattern 16 which consists of the light shielding pattern 3a and the digging pattern 2 formed in the translucent substrate 1 is formed in the transfer pattern formation region 11A. Thereafter, the remaining resist film 6 is removed.
  • the phase shift mask 200 created by the above process includes the digging pattern 2 on the one main surface 11S side of the translucent substrate 1, and the light shielding pattern 3a is formed on the main surface 11S of the translucent substrate 1. It has a structure including the formed light shielding film 3.
  • the engraved pattern 2 is formed on the main surface 11S side of the translucent substrate 1 in a state of being continuous from the opening bottom of the engraved pattern 2 in the transfer pattern forming region 11A of the translucent substrate 1.
  • the transfer pattern 16 composed of the digging pattern 2 and the light shielding pattern 3a is arranged.
  • a hole-shaped alignment pattern 15 penetrating the light shielding film 3 is provided in the outer peripheral region 11B.
  • the chlorine-based gas used in the dry etching during the manufacturing process is not particularly limited as long as it contains Cl.
  • a chlorine-based gas Cl 2, SiCl 2, CHCl 3, CH 2 Cl 2, CCl 4, BCl 3 and the like.
  • the fluorine-based gas used in the dry etching in the manufacturing process is not particularly limited as long as F is contained.
  • a fluorine-based gas CHF 3, CF 4, C 2 F 6, C 4 F 8, SF 6 and the like.
  • the fluorine-based gas not containing C has a relatively low etching rate with respect to the glass substrate, damage to the glass substrate can be further reduced.
  • the phase shift mask 200 is manufactured using the mask blank 100 described with reference to FIG.
  • oxygen-containing chlorine having an isotropic etching tendency in the process of FIG. 2C which is a dry etching process for forming the light shielding pattern 3a (fine pattern) on the light shielding film 3. Dry etching with a system gas is applied. Further, the dry etching with the oxygen-containing chlorine-based gas in the step of FIG. 2C is performed under etching conditions in which the ratio of the chlorine-based gas of the oxygen-containing chlorine-based gas is high and a high bias voltage is applied.
  • the side etching is reduced, and the light shielding pattern 3a formed with high accuracy and the resist film 6 having the digging pattern are used as an etching mask, and the transmissive substrate 1 is dry-etched with a fluorine-based gas, thereby obtaining the digging pattern. 2 and the light-shielding pattern 3a can be formed with high accuracy.
  • the phase shift mask 200 with good pattern accuracy can be manufactured.
  • the semiconductor device manufacturing method is characterized in that the transfer pattern of the phase shift mask 200 is exposed and transferred to the resist film on the substrate using the engraved Levenson type phase shift mask 200 manufactured by the above-described manufacturing method. It is said.
  • the manufacturing method of such a semiconductor device is performed as follows.
  • a substrate for forming a semiconductor device is prepared.
  • This substrate may be, for example, a semiconductor substrate, a substrate having a semiconductor thin film, or a microfabricated film formed thereon.
  • a resist film is formed on the prepared substrate, and pattern exposure is performed on the resist film using the digging Levenson-type phase shift mask 200 manufactured by the above-described manufacturing method. Thereby, the transfer pattern formed on the phase shift mask 200 is exposed and transferred onto the resist film.
  • the exposure light for example, ArF excimer laser light is used here.
  • the resist film to which the transfer pattern is exposed and transferred is developed to form a resist pattern, the surface pattern of the substrate is etched using this resist pattern as a mask, and impurities are introduced. . After the processing is completed, the resist pattern is removed.
  • the semiconductor device is completed by repeatedly performing the above processing on the substrate while exchanging the transfer mask, and further performing necessary processing.
  • a resist pattern with sufficient accuracy to sufficiently satisfy the initial design specifications is formed on the substrate by using the digging Levenson type phase shift mask manufactured by the above-described manufacturing method. be able to. For this reason, when a circuit pattern is formed by dry etching the lower layer film under the resist film using the resist film pattern as a mask, a high-accuracy circuit pattern without wiring short-circuit or disconnection due to insufficient accuracy is formed. Can do.
  • a translucent substrate 1 made of synthetic quartz glass having a main surface dimension of about 152 mm ⁇ about 152 mm and a thickness of about 6.35 mm was prepared.
  • the translucent substrate 1 has its end face and main surface polished to a predetermined surface roughness (root mean square roughness Rq of 0.2 nm or less), and then subjected to a predetermined cleaning process and drying process.
  • the translucent substrate 1 is installed in a single-wafer DC sputtering apparatus, and a mixed gas atmosphere of argon (Ar), carbon dioxide (CO 2 ), and helium (He) is used using a chromium (Cr) target.
  • the reactive sputtering (DC sputtering) was performed.
  • a light shielding film (CrOC film) 3 made of chromium, oxygen, and carbon was formed in a thickness of 59 nm in contact with the translucent substrate 1.
  • a heat treatment was performed on the translucent substrate 1 on which the light shielding film (CrOC film) 3 was formed. Specifically, using a hot plate, heat treatment was performed in the atmosphere at a heating temperature of 280 ° C. and a heating time of 5 minutes. After the heat treatment, the optical density of the light-shielding film 3 at the wavelength of ArF excimer laser light (about 193 nm) is applied to the translucent substrate 1 on which the light-shielding film 3 is formed using a spectrophotometer (Cary 4000 manufactured by Agilent Technologies). As a result, it was confirmed that it was 3.0 or more.
  • the translucent substrate 1 on which the light shielding film 3 is formed is installed in a single wafer RF sputtering apparatus, a silicon dioxide (SiO 2 ) target is used, argon (Ar) gas is used as a sputtering gas, and RF sputtering is performed.
  • a hard mask film 4 made of silicon and oxygen was formed on the light shielding film 3 to a thickness of 12 nm.
  • prescribed washing process was performed and the mask blank 100 of Example 1 was manufactured.
  • a light-shielding film 3 alone was formed on the main surface of another translucent substrate 1 under the same conditions, and a heat treatment was prepared.
  • the light shielding film 3 was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • the region near the surface of the light-shielding film 3 opposite to the translucent substrate 1 side region from the surface to a depth of about 2 nm
  • the content of each constituent element in the region excluding the composition gradient portion of the light shielding film 3 was Cr: 71 atomic%, O: 15 atomic%, and C: 14 atomic% on average. Furthermore, the difference between the constituent elements in the thickness direction of the region excluding the composition gradient portion of the light-shielding film 3 is 3 atomic% or less, and it was confirmed that there is substantially no composition gradient in the thickness direction.
  • FIG. 4 shows the result of analysis of the chemical direction of the Cr2p narrow spectrum in the depth direction obtained by the X-ray photoelectron spectroscopy of the light-shielding film 3 of Example 1.
  • FIG. 4 shows the depth direction of the O1s narrow spectrum.
  • FIG. 5 shows the results of chemical bonding state analysis
  • FIG. 6 shows the results of chemical bonding state analysis in the depth direction of N1s narrow spectrum
  • FIG. 7 shows the results of chemical bonding state analysis in the depth direction of C1s narrow spectrum
  • FIG. The results of chemical bonding state analysis in the depth direction are shown in FIG.
  • the energy distribution of photoelectrons emitted from the light shielding film 3 is measured by irradiating the surface of the light shielding film 3 with X-rays, and the light shielding film 3 is subjected to Ar gas sputtering. Is repeated for a predetermined time, and the step of measuring the energy distribution of photoelectrons emitted from the light shielding film 3 by irradiating the surface of the light shielding film 3 in the dug area with X-rays is repeated.
  • the film thickness direction is analyzed.
  • the position in the film thickness direction of the light shielding film 3 after being dug by Ar gas sputtering from the outermost surface of the light shielding film 3 by 0.80 min is a position deeper than the composition gradient portion. That is, all the plots at the depth positions after the “0.80 min plot” are the measurement results of the portion excluding the composition gradient portion of the light shielding film 3.
  • Example 4 shows that the light shielding film 3 of Example 1 has a maximum peak at a binding energy of 574 eV except for the outermost surface (0.00 min plot). This result means that atoms such as nitrogen and oxygen and unbonded chromium atoms are present in a certain ratio or more.
  • Example 5 shows that the light shielding film 3 of Example 1 has a maximum peak at a binding energy of about 530 eV except the outermost surface (0.00 min plot). This result means that Cr—O bonds are present in a certain ratio or more.
  • Example 7 shows that the light shielding film 3 of Example 1 has a maximum peak at a binding energy of 282 to 283 eV except for the outermost surface (a plot of 0.00 min) from the result of the C1s narrow spectrum in FIG. This result means that Cr—C bonds are present in a certain ratio or more.
  • the engraved Levenson-type phase shift mask 200 of Example 1 was manufactured according to the following procedure.
  • the surface of the hard mask film 4 was subjected to HMDS treatment.
  • a resist film made of a chemically amplified resist for electron beam drawing with a film thickness of 80 nm was formed in contact with the surface of the hard mask film 4 by spin coating.
  • a first pattern which is a light shielding pattern to be formed on the hard mask film 4 is drawn on the resist film with an electron beam, a predetermined development process and a cleaning process are performed, and a resist pattern having the first pattern 5a was formed (see FIG. 2 (a)).
  • This first pattern includes a line and space pattern having a line width of 100 nm.
  • the space width is measured with a CD-SEM (Critical Dimension-Scanning Electron Microscope) in the region where the line and space pattern is formed. It was.
  • a resist film (second resist film) 6 in which a digging pattern is formed is formed on the hard mask film 4 (hard mask pattern 4a) in which a light shielding pattern is formed.
  • a resist film 6 made of a chemically amplified resist for electron beam drawing (PRL009, manufactured by Fuji Film Electronics Materials Co., Ltd.) with a film thickness of 50 nm was formed in contact with the surface of the hard mask film 4 by spin coating. .
  • the film thickness of the resist film 6 is the film thickness on the hard mask film 4.
  • an engraved pattern was drawn on the resist film 6 with an electron beam, and a predetermined development process and a cleaning process for the resist film 6 were performed to form a resist film 6 having an engraved pattern.
  • the opening pattern of the digging pattern formed in the resist film 6 completely exposes the opening of the light shielding pattern 3a. Formed.
  • the light-transmitting substrate 1 using a fluorine-based gas (CF 4 ) was dry-etched using the resist film 6 having a digging pattern as a mask.
  • the digging pattern 2 was formed at a depth of 173 nm in the transfer pattern forming region 11A on the one main surface 11S side of the translucent substrate 1.
  • the resist film 6 decreased in thickness during the dry etching with the fluorine-based gas, and all the resist film 6 on the hard mask film 4 disappeared at the end of the dry etching.
  • the hard mask film 4 was also removed by dry etching with a fluorine-based gas.
  • the remaining resist film 6 was removed, and a process such as cleaning was performed to obtain a phase shift mask 200.
  • the space width was measured with a length-measuring SEM (CD-SEM: Critical-Dimension-Scanning-Electron-Microscope) in the region where the line and space pattern was formed. .
  • an etching bias which is an amount of change between the space width of the hard mask pattern 4a and the space width of the light-shielding pattern 3a measured in advance at a plurality of locations in the region where the same line and space pattern is formed.
  • Each was calculated, and the average value of the etching bias was further calculated.
  • the average value of the etching bias was about 6 nm, which was much smaller than the conventional value.
  • the fine light-shielding pattern can be accurately applied to the light-shielding film. 3 can be formed.
  • Example 2 [Manufacture of mask blanks]
  • the mask blank 100 of Example 2 was manufactured in the same procedure as Example 1 except for the light shielding film 3.
  • the light-shielding film 3 of Example 2 is different from the light-shielding film 3 of Example 1 in film formation conditions.
  • the translucent substrate 1 is installed in a single wafer DC sputtering apparatus, and a mixed gas of argon (Ar), carbon dioxide (CO 2 ), and helium (He) is used using a chromium (Cr) target. Reactive sputtering (DC sputtering) was performed in the atmosphere.
  • a light shielding film (CrOC film) 3 made of chromium, oxygen and carbon was formed in a thickness of 72 nm in contact with the translucent substrate 1.
  • the light-transmitting substrate 1 on which the light shielding film (CrOC film) 3 was formed was subjected to heat treatment under the same conditions as in Example 1.
  • the optical density of the light-shielding film 3 at the wavelength of ArF excimer laser light (about 193 nm) is applied to the translucent substrate 1 on which the light-shielding film 3 is formed using a spectrophotometer (Cary 4000 manufactured by Agilent Technologies). As a result, it was confirmed that it was 3.0 or more.
  • a light-shielding film 3 alone was formed on the main surface of another translucent substrate 1 under the same conditions, and a heat treatment was prepared.
  • the light shielding film 3 was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • the region near the surface of the light-shielding film 3 opposite to the translucent substrate 1 side region from the surface to a depth of about 2 nm
  • the content of each constituent element in the region excluding the composition gradient portion of the light shielding film 3 was Cr: 55 atomic%, O: 30 atomic%, and C: 15 atomic% on average. Furthermore, the difference between the constituent elements in the thickness direction of the region excluding the composition gradient portion of the light-shielding film 3 is 3 atomic% or less, and it was confirmed that there is substantially no composition gradient in the thickness direction.
  • Example 2 With respect to the light-shielding film 3 of Example 2, as a result of the depth direction chemical bond state analysis of Cr2p narrow spectrum (see FIG. 9), the depth direction chemical bond of O1s narrow spectrum is obtained.
  • State analysis result see FIG. 10
  • N1s narrow spectrum depth direction chemical bond state analysis result see FIG. 11
  • C1s narrow spectrum depth direction chemical bond state analysis result see FIG. 12
  • Si2p The result of the chemical analysis of the depth direction of the narrow spectrum was obtained.
  • the result of analysis at the position in the film thickness direction of the light shielding film 3 after digging for 80 min by Ar gas sputtering is “0.80 min plot”, and digging by Ar gas sputtering for 1.60 min from the outermost surface of the light shielding film 3
  • the analysis result at the position in the film thickness direction of the light shielding film 3 after the insertion is 2.8 from the outermost surface of the light shielding film 3 in the “1.60 min plot”.
  • the result of analysis at the position in the film thickness direction of the light shielding film 3 after digging by Ar gas sputtering for min is “2.80 min plot”, and digging by Ar gas sputtering for 3.20 min from the outermost surface of the light shielding film 3
  • the result of analysis at the position in the film thickness direction of the light-shielding film 3 after insertion is shown in the “3.20 min plot”.
  • the position in the film thickness direction of the light shielding film 3 after being dug by Ar gas sputtering from the outermost surface of the light shielding film 3 by 0.80 min is a position deeper than the composition gradient portion. That is, all the plots at the depth positions after the “0.80 min plot” are the measurement results of the portion excluding the composition gradient portion of the light shielding film 3.
  • the light-shielding film 3 of Example 2 has a maximum peak at a binding energy of 574 eV in the region after the depth of “0.80 min plot”. .
  • This result means that atoms such as nitrogen and oxygen and unbonded chromium atoms are present in a certain ratio or more.
  • the light-shielding film 3 of Example 2 has a maximum peak at a binding energy of about 530 eV in the depth region after the “0.80 min plot”. Recognize. This result means that Cr—O bonds are present in a certain ratio or more.
  • the light-shielding film 3 of Example 2 has a maximum peak at a binding energy of 282 to 283 eV in a region having a depth after “0.80 min plot”. I understand. This result means that Cr—C bonds are present in a certain ratio or more.
  • the vertical scales of the graphs in each of the narrow spectra in FIGS. 9 to 13 are not the same.
  • the N1s narrow spectrum in FIG. 11 and the Si2p narrow spectrum in FIG. 13 are greatly expanded in scale on the vertical axis as compared with the narrow spectra in FIGS. 9, 10, and 12.
  • the vibration wave in the graph of the N1s narrow spectrum of FIG. 11 and the Si2p narrow spectrum of FIG. 13 does not show the presence of a peak but only shows noise.
  • phase shift mask 200 of Example 2 was manufactured in the same procedure as in Example 1.
  • the line The space width was measured with a critical dimension SEM (CD-SEM: Critical Dimension Scanning Electron Microscope) in the region where the AND space pattern was formed.
  • an etching bias that is an amount of change between the space width of the hard mask pattern 4a and the space width of the light shielding pattern 3a is calculated, Furthermore, the average value of the etching bias was calculated. As a result, the average value of the etching bias was about 10 nm, which was sufficiently smaller than the conventional value. This means that the mask blank 100 of Example 2 is highly accurate even if the light shielding film 3 is patterned by high bias etching using the hard mask pattern 4a having a fine transfer pattern to be formed on the light shielding film 3 as an etching mask. This shows that the fine transfer pattern can be formed on the light shielding film 3.
  • ⁇ Comparative example 1> [Manufacture of mask blanks]
  • the mask blank of Comparative Example 1 was manufactured in the same procedure as in Example 1 except for the light shielding film.
  • the film forming conditions of the light shielding film of Comparative Example 1 are different from those of the light shielding film 3 of Example 1.
  • a translucent substrate is installed in a single-wafer DC sputtering apparatus, and using a chromium (Cr) target, argon (Ar), carbon dioxide (CO 2 ), nitrogen (N 2 ), and helium ( Reactive sputtering (DC sputtering) in a mixed gas atmosphere of He) was performed.
  • a light shielding film (CrOCN film) made of chromium, oxygen, carbon, and nitrogen was formed in a thickness of 72 nm in contact with the translucent substrate.
  • the light-transmitting substrate on which the light shielding film (CrOCN film) was formed was subjected to heat treatment under the same conditions as in Example 1.
  • the optical density of the light-shielding film at the wavelength of the ArF excimer laser light (about 193 nm) is measured using a spectrophotometer (Cary 4000 manufactured by Agilent Technologies) on the light-transmitting substrate on which the light-shielding film is formed. When measured, it was confirmed that it was 3.0 or more.
  • a light-shielding film alone was formed on the main surface of another translucent substrate under the same conditions, and a heat treatment was prepared.
  • the light shielding film was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • XPS X-ray photoelectron spectroscopy
  • the region near the surface of the light-shielding film opposite to the translucent substrate region from the surface to a depth of about 2 nm
  • each constituent element in the region excluding the composition gradient portion of the light-shielding film is, on average, Cr: 55 atomic%, O: 22 atomic%, C: 12 atomic%, and N: 11 atomic%. all right. Furthermore, the difference in each constituent element in the thickness direction of the region excluding the composition gradient portion of the light-shielding film was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction.
  • the light-shielding film of Comparative Example 1 has a maximum peak with a binding energy greater than 574 eV in the region after the depth of “1.60 min plot”. Recognize. This result means that the abundance ratio of atoms such as nitrogen and oxygen to the bonded chromium atom is considerably small even though it is a so-called chemical shift.
  • phase shift mask of Comparative Example 1 was manufactured in the same procedure as in Example 1.
  • the space width was measured with a CD-SEM (CD-SEM: Critical Dimension-Scanning Electron Microscope). Etching that is the amount of change between the space width of the hard mask pattern and the space width of the light-shielding pattern of the manufactured phase shift mask at a plurality of locations in the region where the same line and space pattern is formed Each bias was calculated, and an average value of the etching bias was calculated.
  • the average value of the etching bias was 20 nm, which was a relatively large value. This is because the mask blank of Comparative Example 1 has a fine transfer with high accuracy when the light shielding film is patterned by high bias etching using a hard mask pattern having a fine transfer pattern to be formed on the light shielding film as an etching mask. This means that it is difficult to form a pattern on the light shielding film.
  • ⁇ Comparative example 2> [Manufacture of mask blanks]
  • the mask blank of Comparative Example 2 was manufactured in the same procedure as in Example 1 except for the light shielding film.
  • the film forming conditions of the light shielding film of Comparative Example 2 are different from those of the light shielding film 3 of Example 1.
  • a translucent substrate is installed in a single-wafer DC sputtering apparatus, and a mixed gas atmosphere of argon (Ar), nitric oxide (NO), and helium (He) using a chromium (Cr) target.
  • Reactive sputtering DC sputtering
  • a light shielding film (CrON film) made of chromium, oxygen and nitrogen was formed in a thickness of 72 nm in contact with the translucent substrate.
  • the light-transmitting substrate on which the light shielding film (CrON film) was formed was subjected to heat treatment under the same conditions as in Example 1.
  • the optical density of the light-shielding film at the wavelength of the light (about 193 nm) of the ArF excimer laser having a laminated structure is used for the light-transmitting substrate on which the light-shielding film is formed, using a spectrophotometer (Cary 4000 manufactured by Agilent Technologies). As a result, it was confirmed that it was 3.0 or more.
  • a light-shielding film alone was formed on the main surface of another translucent substrate under the same conditions, and a heat treatment was prepared.
  • the light shielding film was analyzed by X-ray photoelectron spectroscopy (with XPS and RBS correction).
  • the region near the surface of the light-shielding film on the side opposite to the translucent substrate 1 region from the surface to a depth of about 2 nm
  • each constituent element in the region excluding the composition gradient portion of the light shielding film was Cr: 58 atomic%, O: 17 atomic%, and N: 25 atomic% on average. Furthermore, the difference in each constituent element in the thickness direction of the region excluding the composition gradient portion of the light-shielding film was 3 atomic% or less, and it was confirmed that there was substantially no composition gradient in the thickness direction.
  • the light shielding film of Comparative Example 2 also has a N2s narrow spectrum as a result of a depth direction chemical bond state analysis of the Cr2p narrow spectrum, a depth direction chemical bond state analysis of the O1s narrow spectrum.
  • the depth direction chemical bond state analysis of the C1s narrow spectrum and the depth direction chemical bond state analysis of the Si2p narrow spectrum were obtained.
  • the light-shielding film of Comparative Example 2 has a maximum peak with a binding energy larger than 574 eV in all depth regions including the outermost surface. This result means that the abundance ratio of atoms such as nitrogen and oxygen to the bonded chromium atom is considerably small even though it is a so-called chemical shift. From the results of the O1s narrow spectrum, it was found that the light-shielding film of Comparative Example 2 had a maximum peak at a binding energy of about 530 eV in all depth regions including the outermost surface. This result means that Cr—O bonds are present in a certain ratio or more.
  • the maximum peak of the light-shielding film of Comparative Example 2 is not more than the detection lower limit value except for the outermost surface.
  • the outermost surface is greatly affected by contamination of organic substances, it is difficult to refer to the measurement results regarding carbon for the outermost surface. This result means that in the light-shielding film of Comparative Example 2, the abundance ratio of atoms bonded to carbon including Cr—C bonds was not detected.
  • phase shift mask of Comparative Example 2 was produced in the same procedure as in Example 1.
  • the line-and-line pattern is formed after the hard mask pattern is formed (see FIG. 2B) and after the transfer pattern is formed (see FIG. 3F).
  • the space width was measured with a CD-SEM (CD-SEM: Critical Dimension-Scanning Electron Microscope).
  • Etching that is the amount of change between the space width of the hard mask pattern and the space width of the light-shielding pattern of the manufactured phase shift mask at a plurality of locations in the region where the same line and space pattern is formed Each bias was calculated, and an average value of the etching bias was calculated. As a result, the average value of the etching bias was 30 nm, which was a large value. This is because the mask blank of Comparative Example 2 has a fine transfer with high accuracy when the light shielding film is patterned by high bias etching using a hard mask pattern having a fine transfer pattern to be formed on the light shielding film as an etching mask. This means that it is difficult to form a pattern on the light shielding film.
  • the present invention is not limited to the configuration described in the above embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.
  • the present invention is not limited to this, and may be used for manufacturing a binary mask.

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